Polyfarnesenes

ABSTRACT

Provided herein are polyfarnesenes such as farnesene homopolymers derived from a farnesene and farnesene interpolymers derived from a farnesene and at least a vinyl monomer; and the processes of making and using the polyfarnesenes. The farnesene homopolymer can be prepared by polymerizing the farnesene in the presence of a catalyst. In some embodiments, the farnesene is prepared from a sugar by using a microorganism.

PRIOR RELATED APPLICATIONS

This application is a divisional application of U.S. Non-Provisionalpatent application Ser. No. 12/552,278 filed Sep. 1, 2009, now U.S. Pat.No. 8,048,976 which claims the benefit of U.S. Provisional PatentApplication No. 61/094,059, filed Sep. 4, 2008; U.S. ProvisionalApplication No. 61/220,587, filed Jun. 26, 2009; and U.S. ProvisionalApplication No. 61/220,588, filed Jun. 26, 2009, all of which areincorporated herein by reference in their entirety.

FIELD OF THE INVENTION

This invention provides polyfarnesenes such as farnesene homopolymersderived from a farnesene and farnesene interpolymers derived from afarnesene and at least a vinyl monomer; and the processes of making andusing the polyfarnesenes disclosed herein.

BACKGROUND OF THE INVENTION

Terpenes or isoprenoid compounds are a large and varied class of organicmolecules that can be produced by a wide variety of plants, such asconifers, and by some insects, such as swallowtail butterflies. Someisoprenoid compounds can also be made from organic compounds such assugars by microorganisms, including bioengineered microorganisms.Because terpenes or isoprenoid compounds can be obtained from variousrenewable sources, they are ideal monomers for making eco-friendly andrenewable polymers.

Terpene polymers derived from terpenes or isoprenoid compounds areuseful polymeric materials. For example, polyisoprene, polypinene andpolylimonene have been used in various applications such as in themanufacture of paper coatings, adhesives, rubber compounds, and otherindustrial products. Most existing terpene polymers are generallyderived from C₅ and C₁₀ terpenes, for example, isoprene, limonene,myrcene, 3-carene, ocimene, and pinene. These terpene monomers can bepolymerized or co-polymerized with other comonomers to form thecorresponding terpene homopolymers or copolymers. However, the polymersor copolymers of terpenes or isoprenoid compounds having at least 15carbon atoms are less well known or non-existent. Because of their longchain length, isoprenoid compounds, such as farnesene, farnesol,nerolidol, valencene, humulene, germacrene, and elemene, may providepolymers or copolymers with unique physical, chemical and biologicalproperties.

There is a need for more environmentally friendly and/or renewablepolymers, for instance, polymers derived from isoprenoid compounds thatcan be obtained from natural sources. Further, there is also a need fornovel polymers that have unique physical, chemical and biologicalproperties.

SUMMARY OF THE INVENTION

The aforementioned needs are met by various aspects disclosed herein. Inone aspect, provided herein is a polyfarnesene comprising one or moreunits having formula (I), (II), (III), (IV) or a combination thereof:

wherein R¹ has formula (XI):

R² has formula (XII):

wherein each of m, n, l and k is an integer from 1 to 100,000; andwherein the amount of formula (I) is at most about 80 wt. %, based onthe total weight of the polyfarnesene.

In another aspect, provided herein is a polyfarnesene comprising one ormore units having formula (V), (VI), (VII), (VIII) or a combinationthereof:

wherein R³ has formula (XIII):

R⁴ has formula (XIV):

wherein each of m, n, l and k is an integer from 1 to 100,000.

In some embodiments, the polyfarnesene disclosed herein furthercomprises one or more units having formula (IX):

wherein p is an integer from 1 to 100,000; and each of R⁵, R⁶, R⁷ and R⁸is independently H, alkyl, cycloalkyl, aryl, alkenyl, cycloalkenyl,alkynyl, heterocyclyl, alkoxy, aryloxy, carboxy, alkoxycarbonyl,aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, acyloxy,nitrile or halo.

In certain embodiments, the polyfarnesene disclosed herein is a randominterpolymer. In other embodiments, the polyfarnesene disclosed hereinis a block interpolymer having one or more first blocks and one or moresecond blocks, wherein each of the one or more first blocks comprisesthe one or more units having formula (I), (II), (III), (IV) or acombination thereof and wherein each of the one or more second blockscomprises the unit having formula (IX). In further embodiments, thepolyfarnesene disclosed herein is a block interpolymer having one ormore first blocks and one or more second blocks, wherein each of the oneor more first blocks comprises the one or more units having formula (V),(VI), (VII), (VIII) or a combination thereof and wherein each of the oneor more second blocks comprises the unit having formula (IX).

In certain embodiments, the block interpolymer disclosed hereincomprises one first block and two second blocks wherein the first blockis between the two second blocks. In other embodiments, R⁵ of formula(IX) is aryl; and each of R⁶, R⁷ and R⁸ of formula (IX) is H. In stillfurther embodiments, R⁵ of formula (IX) is phenyl.

In some embodiments, the amount of formula (III) in the polyfarnesenedisclosed herein is at least about 20 wt. %, based on the total weightof the polyfarnesene. In other embodiments, the total amount of formulae(V) and (VI) in the polyfarnesene disclosed herein is from about 1 wt. %to about 99 wt. %, based on the total weight of the polyfarnesene. Infurther embodiments, the amount of formula (VII) in the polyfarnesenedisclosed herein is from about 1 wt. % to about 99 wt. %, based on thetotal weight of the polyfarnesene.

In certain embodiments, the sum of m, n and l of the polyfarnesenedisclosed herein is greater than about 300, greater than about 500 orgreater than about 1000. In other embodiments, the number-averagemolecular weight (M_(n)) of the polyfarnesene disclosed herein isgreater than about 100,000 daltons, greater than 500,000 daltons,greater than 1,000,000 daltons, greater than 1,500,000 daltons orgreater than 2,000,000 daltons. In further embodiments, thepolyfarnesene disclosed herein has at least one glass transitiontemperature (T_(g)) of less than −55° C., less than −60° C. or less than−65° C.

In another aspect, provided herein is a polyfarnesene prepared bypolymerizing a β-farnesene in the presence of a catalyst, wherein theamount of the cis-1,4-microstructure in the polyfarnesene is at mostabout 80 wt. %, based on the total weight of the polyfarnesene. In someembodiments, the β-farnesene is copolymerized with a vinyl monomer toform a farnesene copolymer. In further embodiments, the β-farnesene isprepared by a microorganism. In further embodiments, the β-farnesene isderived from a simple sugar.

In another aspect, provided herein is a polyfarnesene prepared bypolymerizing an α-farnesene in the presence of a catalyst, wherein theamount of the cis-1,4-microstructure in the polyfarnesene is from about1 wt. % to about 99 wt. %, based on the total weight of thepolyfarnesene. In some embodiments, the α-farnesene is copolymerizedwith a vinyl monomer to form a farnesene copolymer. In furtherembodiments, the α-farnesene is prepared by a microorganism. In furtherembodiments, the α-farnesene is derived from a simple sugar.

In certain embodiments, the vinyl monomer is styrene. In otherembodiments, the polyfarnesene is a block copolymer.

In another aspect, provided herein is a saturated polyfarnesene preparedby (a) polymerizing a farnesene in the presence of a catalyst to form apolyfarnesene; and (b) hydrogenating at least a portion of the doublebonds in the polyfarnesene in the presence of a hydrogenation reagent.In some embodiments, the farnesene is copolymerized with a vinyl monomerto form a farnesene copolymer. In other embodiments, the vinyl monomeris styrene. In further embodiments, the polyfarnesene is a blockcopolymer. In still further embodiments, the farnesene is α-farnesene orβ-farnesene or a combination thereof.

In some embodiments, the catalyst disclosed herein comprises anorganolithium reagent. In other embodiments, the catalyst furthercomprises a polar modifier such as 1,2-bis(dimethylamino)ethane. Infurther embodiments, the organolithium reagent is n-butyl lithium orsec-butyl lithium.

In certain embodiments, the hydrogenation reagent is hydrogen in thepresence of a hydrogenation catalyst. In other embodiments, thehydrogenation catalyst is 10% Pd/C.

Additional aspects of the invention and characteristics and propertiesof various embodiments of the invention become apparent with thefollowing description.

DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts Ultraviolet-Visible (UV-Vis) spectra of Example 1 andβ-farnesene.

FIG. 2 depicts a Gel Permeation Chromatography (GPC) curve of Example 1.

FIG. 3 depicts a C¹³ Nuclear Magnetic Resonance (NMR) spectrum ofExample 1.

FIG. 4 depicts a H¹ NMR spectrum of Example 1.

FIG. 5 depicts a Differential Scanning calorimetry (DSC) curve ofExample 1.

FIG. 6 depicts a Thermal Gravimetric Analysis (TGA) curve of Example 1measured in air.

FIG. 7 depicts a Thermal Gravimetric Analysis (TGA) curve of Example 1measured in nitrogen.

FIG. 8 depicts lap test results of Example 1.

FIG. 9 depicts a GPC curve of Example 2.

FIG. 10 depicts a DSC curve of Example 2.

FIG. 11 depicts tensile test results of Example 2.

FIG. 12 depicts a GPC curve of Example 3.

FIG. 13 depicts a C¹³ NMR spectrum of Example 3.

FIG. 14 depicts a H¹ NMR spectrum of Example 3.

FIG. 15 depicts a DSC curve of Example 3.

FIG. 16 depicts a TGA curve of Example 3.

FIG. 17 depicts lap test results of Example 3.

FIG. 18 depicts a GPC curve of polystyrene formed.

FIG. 19 depicts a GPC curve of polystyrene-1,4-polyfarnesene di-blockcopolymer formed.

FIG. 20 depicts a GPC curve of Example 4.

FIG. 21 depicts a ¹³C NMR spectrum of Example 4.

FIG. 22 depicts a ¹H NMR spectrum of Example 4.

FIG. 23 depicts a DSC curve of Example 4.

FIG. 24 depicts a TGA curve of Example 4.

FIG. 25 depicts tensile test results of Example 4.

FIG. 26 depicts lap test results of Example 4.

FIG. 27 depicts a GPC curve of polystyrene formed.

FIG. 28 depicts a GPC curve of polystyrene-3,4-polyfarnesene di-blockcopolymer formed.

FIG. 29 depicts a GPC curve of Example 5.

FIG. 30 depicts a ¹³C NMR spectrum of Example 5.

FIG. 31 depicts a ¹H NMR spectrum of Example 5.

FIG. 32 depicts a DSC curve of Example 5.

FIG. 33 depicts a TGA curve of Example 5.

FIG. 34 depicts tensile test results of Example 5.

FIG. 35 depicts a GPC curve of Example 5 after extraction with hexane.

FIG. 36 depicts a GPC curve of hexane after extraction for Example 5.

FIG. 37 depicts tensile test results of Example 5.

FIG. 38 depicts lap test results of Example 5.

FIG. 39 depicts tensile test results of Example 6.

FIG. 40 depicts tensile test results of Example 7.

DETAILED DESCRIPTION OF THE INVENTION General Definitions

“Polymer” refers to a polymeric compound prepared by polymerizingmonomers, whether of the same or a different type. The generic term“polymer” embraces the terms “homopolymer,” “copolymer,” “terpolymer” aswell as “interpolymer.”

“Interpolymer” refers to a polymer prepared by the polymerization of atleast two different types of monomers. The generic term “interpolymer”includes the term “copolymer” (which generally refers to a polymerprepared from two different monomers) as well as the term “terpolymer”(which generally refers to a polymer prepared from three different typesof monomers). It also encompasses polymers made by polymerizing four ormore types of monomers.

“Organyl” refers to any organic substituent group, regardless offunctional type, having one free valence at a carbon atom, e.g.,CH₃CH₂—, ClCH₂—, CH₃C(═O)—, 4-pyridylmethyl.

“Hydrocarbyl” refers to any univalent group formed by removing ahydrogen atom from a hydrocarbon, such as alkyl (e.g., ethyl),cycloalkyl (e.g., cyclohexyl) and aryl (e.g., phenyl).

“Heterocyclyl” refers to any univalent group formed by removing ahydrogen atom from any ring atom of a heterocyclic compound.

“Alkyl” or “alkyl group” refers to a univalent group having the generalformula C_(n)H_(2n+1) derived from removing a hydrogen atom from asaturated, unbranched or branched aliphatic hydrocarbon, where n is aninteger, or an integer between 1 and 20, or between 1 and 8. Examples ofalkyl groups include, but are not limited to, (C₁-C₈)alkyl groups, suchas methyl, ethyl, propyl, isopropyl, 2-methyl-1-propyl,2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl,2,2-dimethyl-1-propyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl,4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl,4-methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl,2-ethyl-1-butyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl,hexyl, heptyl and octyl. Longer alkyl groups include nonyl and decylgroups. An alkyl group can be unsubstituted or substituted with one ormore suitable substituents. Furthermore, the alkyl group can be branchedor unbranched. In some embodiments, the alkyl group contains at least 2,3, 4, 5, 6, 7, or 8 carbon atoms.

“Cycloalkyl” or “cycloalkyl group” refers to a univalent group derivedfrom a cycloalkane by removal of a hydrogen atom from a non-aromatic,monocyclic or polycyclic ring comprising carbon and hydrogen atoms.Examples of cycloalkyl groups include, but are not limited to,(C₃-C₇)cycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, and cycloheptyl, and saturated cyclic and bicyclic terpenesand (C₃-C₇)cycloalkenyl groups, such as cyclopropenyl, cyclobutenyl,cyclopentenyl, cyclohexenyl, and cycloheptenyl, and unsaturated cyclicand bicyclic terpenes. A cycloalkyl group can be unsubstituted orsubstituted by one or two suitable substituents. Furthermore, thecycloalkyl group can be monocyclic or polycyclic. In some embodiments,the cycloalkyl group contains at least 5, 6, 7, 8, 9, or 10 carbonatoms.

“Aryl” or “aryl group” refers to an organic radical derived from amonocyclic or polycyclic aromatic hydrocarbon by removing a hydrogenatom. Non-limiting examples of the aryl group include phenyl, naphthyl,benzyl, or tolanyl group, sexiphenylene, phenanthrenyl, anthracenyl,coronenyl, and tolanylphenyl. An aryl group can be unsubstituted orsubstituted with one or more suitable substituents. Furthermore, thearyl group can be monocyclic or polycyclic. In some embodiments, thearyl group contains at least 6, 7, 8, 9, or 10 carbon atoms.

“Isoprenoid” and “isoprenoid compound” are used interchangeably hereinand refer to a compound derivable from isopentenyl diphosphate.

“Substituted” as used to describe a compound or chemical moiety refersto that at least one hydrogen atom of that compound or chemical moietyis replaced with a second chemical moiety. The second chemical moietycan be any desired substituent that does not adversely affect thedesired activity of the compound. Examples of substituents are thosefound in the exemplary compounds and embodiments disclosed herein, aswell as halogen; alkyl; heteroalkyl; alkenyl; alkynyl; aryl, heteroaryl,hydroxyl; alkoxyl; amino; nitro; thiol; thioether; imine; cyano; amido;phosphonato; phosphine; carboxyl; thiocarbonyl; sulfonyl; sulfonamide;acyl; formyl; acyloxy; alkoxycarbonyl; oxo; haloalkyl (e.g.,trifluoromethyl); carbocyclic cycloalkyl, which can be monocyclic orfused or non-fused polycyclic (e.g., cyclopropyl, cyclobutyl,cyclopentyl or cyclohexyl) or a heterocycloalkyl, which can bemonocyclic or fused or non-fused polycyclic (e.g., pyrrolidinyl,piperidinyl, piperazinyl, morpholinyl or thiazinyl); carbocyclic orheterocyclic, monocyclic or fused or non-fused polycyclic aryl (e.g.,phenyl, naphthyl, pyrrolyl, indolyl, furanyl, thiophenyl, imidazolyl,oxazolyl, isoxazolyl, thiazolyl, triazolyl, tetrazolyl, pyrazolyl,pyridinyl, quinolinyl, isoquinolinyl, acridinyl, pyrazinyl, pyridazinyl,pyrimidinyl, benzimidazolyl, benzothiophenyl or benzofuranyl); amino(primary, secondary or tertiary); o-lower alkyl; o-aryl, aryl;aryl-lower alkyl; —CO₂CH₃; —CONH₂; —OCH₂CONH₂; —NH₂; —SO₂NH₂; —OCHF₂;—CF₃; —OCF₃; —NH(alkyl); —N(alkyl)₂; —NH(aryl); —N(alkyl)(aryl);—N(aryl)₂; —CHO; —CO(alkyl); —CO(aryl); —CO₂(alkyl); and —CO₂(aryl); andsuch moieties can also be optionally substituted by a fused-ringstructure or bridge, for example —OCH₂O—. These substituents canoptionally be further substituted with a substituent selected from suchgroups. All chemical groups disclosed herein can be substituted, unlessit is specified otherwise.

“Organolithium reagent” refers to an organometallic compound with adirect bond between a carbon and a lithium atom. Some non-limitingexamples of organolithium reagents include vinyllithium, aryllithium(e.g., phenyllithium), and alkyllithium (e.g., n-butyl lithium,sec-butyl lithium, tert-butyl lithium, methyllithium, isopropyllithiumor other alkyllithium reagents having 1 to 20 carbon atoms).

A composition that is “substantially free” of a compound means that thecomposition contains less than about 20 wt. %, less than about 10 wt. %,less than about 5 wt. %, less than about 3 wt. %, less than about 1 wt.%, less than about 0.5 wt. %, less than about 0.1 wt. %, or less thanabout 0.01 wt. % of the compound, based on the total volume of thecomposition.

A polymer that is “substantially linear” means that the polymer containsless than about 20 wt. %, less than about 10 wt. %, less than about 5wt. %, less than about 3 wt. %, less than about 1 wt. %, less than about0.5 wt. %, less than about 0.1 wt. %, or less than about 0.01 wt. % ofthe branched, star-shaped or other regular or irregular structures,based on the total volume of the composition.

A polymer that is “substantially branched” means that the polymercontains less than about 20 wt. %, less than about 10 wt. %, less thanabout 5 wt. %, less than about 3 wt. %, less than about 1 wt. %, lessthan about 0.5 wt. %, less than about 0.1 wt. %, or less than about 0.01wt. % of the linear, star-shaped or other regular or irregularstructures, based on the total volume of the composition.

A polymer that is “substantially star-shaped” means that the polymercontains less than about 20 wt. %, less than about 10 wt. %, less thanabout 5 wt. %, less than about 3 wt. %, less than about 1 wt. %, lessthan about 0.5 wt. %, less than about 0.1 wt. %, or less than about 0.01wt. % of the branched, linear or other regular or irregular structures,based on the total volume of the composition.

In the following description, all numbers disclosed herein areapproximate values, regardless whether the word “about” or “approximate”is used in connection therewith. They may vary by 1 percent, 2 percent,5 percent, or, sometimes, 10 to 20 percent. Whenever a numerical rangewith a lower limit, R^(L), and an upper limit, R^(U), is disclosed, anynumber falling within the range is specifically disclosed. Inparticular, the following numbers within the range are specificallydisclosed: R=R^(L)+k*(R^(U)−R^(L)), wherein k is a variable ranging from1 percent to 100 percent with a 1 percent increment, i.e., k is 1percent, 2 percent, 3 percent, 4 percent, 5 percent, . . . , 50 percent,51 percent, 52 percent, . . . , 95 percent, 96 percent, 97 percent, 98percent, 99 percent, or 100 percent. Moreover, any numerical rangedefined by two R numbers as defined in the above is also specificallydisclosed.

The compositions disclosed herein generally comprise a polyfarnesene andoptionally a tackifier. In other embodiments, the compositions disclosedherein do not comprise a tackifier. In further embodiments, thecompositions disclosed herein comprise a tackifier.

In some embodiments, the polyfarnesene is a farnesene homopolymer, afarnesene interpolymer or a combination thereof. In certain embodiments,the polyfarnesene is a farnesene homopolymer comprising units derivedfrom at least one farnesene such as α-farnesene, β-farnesene or acombination thereof. In other embodiments, the polyfarnesene is afarnesene interpolymer comprising units derived from at least onefarnesene and units derived from at least one copolymerizable vinylmonomer. In further embodiments, the farnesene interpolymer is derivedfrom styrene and at least one farnesene. In still further embodiments,the farnesene interpolymer is a random, block or alternatinginterpolymer. In still further embodiments, the farnesene interpolymeris a di-block, tri-block or other multi-block interpolymer.

In some embodiments, the farnesene homopolymer is prepared bypolymerizing β-farnesene in the presence of any catalyst suitable forpolymerizing olefins such as ethylene, styrene or isoprene. In otherembodiments, the farnesene homopolymer comprises one or more unitshaving formula (I), (II), (III), (IV), a stereoisomer thereof or acombination thereof:

wherein R¹ has formula (XI):

R² has formula (XII):

wherein each of m, n, l and k is independently an integer from 1 toabout 5,000, from 1 to about 10,000, from 1 to about 50,000, from 1 toabout 100,000, from 1 to about 200,000, from 1 to about 500,000, from 2to about 10,000, from 2 to about 50,000, from 2 to about 100,000, from 2to about 200,000, or from 2 to about 500,000. In some embodiments, eachof m, n, l and k is independently an integer from 1 to 100,000. In otherembodiments, each of m, n, l and k is independently an integer from 2 to100,000.

In certain embodiments, the farnesene homopolymer comprises at least oneunit having formula (I) wherein m is greater than about 300, greaterthan about 500 or greater than about 1000. In other embodiments, thefarnesene homopolymer comprises at least one unit having formula (II)wherein n is greater than about 300, greater than about 500 or greaterthan about 1000. In further embodiments, the farnesene homopolymercomprises at least one unit having formula (III) wherein l is greaterthan about 300, greater than about 500 or greater than about 1000. Instill further embodiments, the farnesene homopolymer comprises at leastone unit having formula (IV) wherein k is greater than about 300,greater than about 500 or greater than about 1000.

In some embodiments, the farnesene homopolymer comprises at least oneunit having formula (I) and at least one unit having formula (II),wherein the sum of m and n is greater than about 300, greater than about500 or greater than about 1000. In other embodiments, the farnesenehomopolymer comprises at least one unit having formula (I) and at leastone unit having formula (III), wherein the sum of m and l is greaterthan about 300, greater than about 500 or greater than about 1000. Inother embodiments, the farnesene homopolymer comprises at least one unithaving formula (II) and at least one unit having formula (III), whereinthe sum of n and l is greater than about 300, greater than about 500 orgreater than about 1000. In still further embodiments, the farnesenehomopolymer comprises at least one unit having formula (I), at least oneunit having formula (II) and at least one unit having formula (III),wherein the sum of m, n and l is greater than about 300, greater thanabout 500 or greater than about 1000. In still further embodiments, thefarnesene homopolymer comprises at least one unit having formula (I), atleast one unit having formula (II), at least one unit having formula(III) and at least one unit having formula (IV), wherein the sum of m,n, l and k is greater than about 300, greater than about 500 or greaterthan about 1000. In still further embodiments, the one or more unitshaving formula (I), (II), (III) or (IV) in the farnesene homopolymerdisclosed herein can be in any order.

In certain embodiments, the farnesene homopolymer is prepared bypolymerizing α-farnesene in the presence of any catalyst suitable forpolymerizing olefins. In other embodiments, the farnesene homopolymercomprises one or more units having formula (V), (VI), (VII), (VIII), astereoisomer thereof or a combination thereof:

wherein R³ has formula (XIII):

R⁴ has formula (XIV):

wherein each of m, n, l and k is independently an integer from 1 toabout 5,000, from 1 to about 10,000, from 1 to about 50,000, from 1 toabout 100,000, from 1 to about 200,000, from 1 to about 500,000, from 2to about 10,000, from 2 to about 50,000, from 2 to about 100,000, from 2to about 200,000, or from 2 to about 500,000. In some embodiments, eachof m, n, l and k is independently an integer from 1 to 100,000. In otherembodiments, each of m, n, l and k is independently an integer from 2 to100,000.

In certain embodiments, the farnesene homopolymer comprises at least oneunit having formula (V) wherein m is greater than about 300, greaterthan about 500 or greater than about 1000. In other embodiments, thefarnesene homopolymer comprises at least one unit having formula (VI)wherein n is greater than about 300, greater than about 500 or greaterthan about 1000. In further embodiments, the farnesene homopolymercomprises at least one unit having formula (VII) wherein l is greaterthan about 300, greater than about 500 or greater than about 1000. Instill further embodiments, the farnesene homopolymer comprises at leastone unit having formula (VIII) wherein k is greater than about 300,greater than about 500 or greater than about 1000.

In some embodiments, the farnesene homopolymer comprises at least oneunit having formula (V) and at least one unit having formula (VI),wherein the sum of m and n is greater than about 300, greater than about500 or greater than about 1000. In other embodiments, the farnesenehomopolymer comprises at least one unit having formula (V) and at leastone unit having formula (VII), wherein the sum of m and l is greaterthan about 300, greater than about 500 or greater than about 1000. Inother embodiments, the farnesene homopolymer comprises at least one unithaving formula (VI) and at least one unit having formula (VII), whereinthe sum of n and l is greater than about 300, greater than about 500 orgreater than about 1000. In still further embodiments, the farnesenehomopolymer comprises at least one unit having formula (V), at least oneunit having formula (VI) and at least one unit having formula (VII),wherein the sum of m, n and l is greater than about 300, greater thanabout 500 or greater than about 1000. In still further embodiments, thefarnesene homopolymer comprises at least one unit having formula (V), atleast one unit having formula (VI), at least one unit having formula(VII) and at least one unit having formula (VIII), wherein the sum of m,n, l and k is greater than about 300, greater than about 500 or greaterthan about 1000. In still further embodiments, the one or more unitshaving formula (V), (VI), (VII) or (VIII) in the farnesene homopolymerdisclosed herein can be in any order.

In some embodiments, the farnesene homopolymer is prepared bypolymerizing a mixture of α-farnesene and β-farnesene in the presence ofany catalyst suitable for polymerizing olefins. In other embodiments,the farnesene homopolymer comprises one or more units having formula(I), (II), (III), (IV), (V), (VI), (VII) or (VIII) disclosed herein, astereoisomer thereof or a combination thereof. In further embodiments,the one or more units having formula (I), (II), (III), (IV), (V), (VI),(VII) or (VIII) in the farnesene homopolymer disclosed herein can be inany order.

In some embodiments, the farnesene homopolymer comprises two or moreunits having two different formulae selected from formulae (I), (II),(III), (IV), (V), (VI), (VII), (VIII), stereoisomers thereof andcombinations thereof. In other embodiments, such farnesene homopolymercan be represented by the following formula: A_(x)B_(y) wherein each ofx and y is at least 1, and wherein each of A and B independently hasformula (I), (II), (III), (IV), (V), (VI), (VII) or (VIII) and A and Bare different. In further embodiment, each of x and y is independentlygreater than 1, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35,40, or higher. In some embodiment, the As and Bs are linked in asubstantially linear fashion, as opposed to a substantially branched orsubstantially star-shaped fashion. In other embodiments, the As and Bsare randomly distributed along the farnesene homopolymer chain. In otherembodiments, the As and Bs are in two “segments” to provide a farnesenehomopolymer having a segmented structure, for example, AA--A-BB---B. Inother embodiments, the As and Bs are alternatively distributed along thefarnesene homopolymer chain to provide a farnesene homopolymer having analternative structure, for example, A-B, A-B-A, A-B-A-B, A-B-A-B-A orthe like.

In some embodiments, the farnesene homopolymer comprises three or moreunits having three different formulae selected from formulae (I), (II),(III), (IV), (V), (VI), (VII), (VIII), stereoisomers thereof andcombinations thereof. In other embodiments, such farnesene homopolymercan be represented by the following formula: A_(x)B_(y)C_(z) whereineach of x, y and z is at least 1, and wherein each of A, B and Cindependently has formula (I), (II), (III), (IV), (V), (VI), (VII) or(VIII) and A, B and C are different. In further embodiment, each of x, yand z is independently greater than 1, such as 2, 3, 4, 5, 6, 7, 8, 9,10, 15, 20, 25, 30, 35, 40, or higher. In some embodiment, the As, Bsand Cs are linked in a substantially linear fashion, as opposed to asubstantially branched or substantially star-shaped fashion. In otherembodiments, the As, Bs and Cs are randomly distributed along thefarnesene homopolymer chain. In other embodiments, the As, Bs and Cs arein three “segments” to provide a farnesene homopolymer having asegmented structure, for example, AA--A-BB--B-CC--C. In otherembodiments, the As, Bs and Cs are alternatively distributed along thefarnesene homopolymer chain to provide a farnesene homopolymer having analternative structure, for example, A-B-C-A-B, A-B-C-A-B-C or the like.

In certain embodiments, the polyfarnesene is a farnesene interpolymer.In other embodiments, the farnesene interpolymer is prepared bypolymerizing at least one farnesene and at least one vinyl monomer inthe presence of any catalyst suitable for polymerizing olefins and vinylmonomers. In further embodiments, the farnesene interpolymer disclosedherein comprises (a) one or more units having at least one of formulae(I), (II), (III) and (IV) disclosed herein; and (b) one or more unitshaving formula (IX):

wherein p is an integer from 1 to about 5,000, from 1 to about 10,000,from 1 to about 50,000, from 1 to about 100,000, from 1 to about200,000, from 1 to about 500,000, from 2 to about 10,000, from 2 toabout 50,000, from 2 to about 100,000, from 2 to about 200,000, or from2 to about 500,000; and each of R⁵, R⁶, R⁷ and R⁸ is independently H, anorganyl group, or a functional group. In some embodiments, each of R⁵,R⁶, R⁷ and R⁸ is not a monovalent hydrocarbon group containing 4-8carbon atoms. In some embodiments, each of R⁵, R⁶, R⁷ and R⁸ is not analkyl group containing 4-8 carbon atoms.

In some embodiments, the farnesene interpolymer disclosed hereincomprises (a) one or more units having at least one of formulae (V),(VI), (VII) and (VIII) disclosed herein; and (b) one or more unitshaving formula (IX) disclosed herein. In other embodiments, thefarnesene interpolymer disclosed herein comprises (a) one or more unitshaving at least one of formulae (I), (II), (III), (IV), (V), (VI), (VII)and (VIII) disclosed herein; and (b) one or more units having formula(IX) disclosed herein.

In some embodiments, the farnesene interpolymer disclosed herein is arandom interpolymer. In other embodiments, the farnesene interpolymerdisclosed herein is a random interpolymer wherein the vinyl monomerunits and the farnesene units are randomly distributed. In furtherembodiments, the farnesene interpolymer disclosed herein is a randominterpolymer wherein the vinyl monomer units and the farnesene units arerandomly distributed and wherein two or more of formulae (I), (II),(III), (IV), (V), (VI), (VII), (VIII) and (XI) in the farnesene unitsare distributed randomly, alternatively or in blocks.

In some embodiments, the farnesene interpolymer disclosed herein is analternating interpolymer. In other embodiments, the farneseneinterpolymer disclosed herein is an alternating interpolymer wherein thevinyl monomer units and the farnesene units are alternativelydistributed. In further embodiments, the farnesene interpolymerdisclosed herein is an alternating interpolymer wherein the vinylmonomer units and the farnesene units are alternatively distributed andwherein two or more of formulae (I), (II), (III), (IV), (V), (VI),(VII), (VIII) and (XI) in the farnesene units are distributed randomly,alternatively or in blocks.

In certain embodiments, the farnesene interpolymer is a blockinterpolymer having one or more first blocks comprising the one or moreunits having formula (I), (II), (III), (IV) or a combination thereof andone or more second blocks comprising the one or more units havingformula (IX). In further embodiments, the farnesene interpolymer is ablock interpolymer having one or more first blocks comprising the one ormore units having formula (V), (VI), (VII), (VIII) or a combinationthereof and one or more second blocks comprising the one or more unitshaving formula (IX). In still further embodiments, there are one firstblock and two second blocks and wherein the first block is between thetwo second blocks. In still further embodiments, each of the secondblocks comprises units derived from styrene. In some embodiments, thefarnesene block interpolymer is a polystyrene-polyfarnesene di-blockpolyfarnesene, polystyrene-polyfarnesene-polystyrene tri-blockpolyfarnesene or a combination thereof.

In some embodiments, the farnesene interpolymer can be represented bythe following formula: P_(x)Q_(y) wherein each of x and y is at least 1,and wherein P has formula (IX) and Q has formula (I), (II), (III), (IV),(V), (VI), (VII) or (VIII). In further embodiment, each of x and y isindependently greater than 1, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 15,20, 25, 30, 35, 40, or higher. In some embodiment, the Ps and Qs arelinked in a substantially linear fashion, as opposed to a substantiallybranched or substantially star-shaped fashion. In other embodiments, thePs and Qs are randomly distributed along the farnesene interpolymerchain. In other embodiments, the Ps and Qs are in two or more blocks orsegments to provide a farnesene interpolymer having a block structure,for example, PP--P-QQ---Q or PP--P-QQ---Q-P---PP. In other embodiments,the Ps and Qs are alternatively distributed along the farneseneinterpolymer chain to provide a farnesene interpolymer having analternative structure, for example, P-Q, P-Q-P, P-Q-P-Q, P-Q-P-Q-P orthe like. In some embodiments, each Q has formula A_(x)B_(y) orA_(x)B_(y)C_(z) as disclosed herein.

In certain embodiments, the amount of formula (I) in the polyfarnesenedisclosed herein is at most about 85 wt. %, at most about 80 wt. %, atmost about 70 wt. %, at most about 60 wt. %, or at most about 50 wt. %,based on the total weight of the polyfarnesene. In other embodiments,the amount of formula (III) in the polyfarnesene disclosed herein is atleast about 10 wt. %, at least about 15 wt. %, at least about 20 wt. %,at least about 25 wt. %, at least about 30 wt. %, at least about 40 wt.%, at least about 50 wt. %, at least about 60 wt. %, at least about 70wt. %, at least about 80 wt. %, at least about 90 wt. %, at least about95 wt. %, or at least about 99 wt. %, based on the total weight of thepolyfarnesene. In further embodiments, the amount of formula (II) in thepolyfarnesene disclosed herein is from about 1 wt. % to about 99 wt. %,from about 5 wt. % to about 99 wt. %, from about 10 wt. % to about 99wt. %, or from about 15 wt. % to about 99 wt. %, based on the totalweight of the polyfarnesene. In still further embodiments, the amount offormula (IV) in the polyfarnesene disclosed herein is at most about 0.1wt. %, at most about 0.5 wt. %, at most about 1 wt. %, at most about 2wt. %, or at most about 3 wt. %, based on the total weight of thepolyfarnesene. In some embodiments, the polyfarnesene disclosed hereinis substantially free of formula (I), (II), (III) or (IV).

In certain embodiments, the amount of formula (V), (VI), (VII) or (VIII)in the polyfarnesene disclosed herein is at most about 1 wt. %, at mostabout 5 wt. %, at most about 10 wt. %, at most about 20 wt. %, at mostabout 30 wt. %, at most about 40 wt. %, at most about 50 wt. %, at mostabout 60 wt. %, at most about 70 wt. %, at most about 80 wt. %, or atmost about 90 wt. %, based on the total weight of the polyfarnesene. Inother embodiments, the amount of formula (V), (VI), (VII) or (VIII) inthe polyfarnesene disclosed herein is at least about 1 wt. %, at leastabout 2 wt. %, at least about 3 wt. %, at least about 5 wt. %, at leastabout 10 wt. %, at least about 20 wt. %, at least about 30 wt. %, atleast about 40 wt. %, at least about 50 wt. %, at least about 60 wt. %,based on the total weight of the polyfarnesene. In further embodiments,the amount of formula (V), (VI), (VII) or (VIII) in the polyfarnesenedisclosed herein is from about 1 wt. % to about 99 wt. %, from about 5wt. % to about 99 wt. %, from about 10 wt. % to about 99 wt. %, or fromabout 15 wt. % to about 99 wt. %, based on the total weight of thepolyfarnesene. In some embodiments, the polyfarnesene disclosed hereinis substantially free of formula (V), (VI), (VII) or (VIII).

In other embodiments, the sum of m and n disclosed herein is greaterthan about 250, greater than about 300, greater than about 500, greaterthan about 750, greater than about 1000, or greater than about 2000. Infurther embodiments, the sum of m and 1 disclosed herein is greater thanabout 250, greater than about 300, greater than about 500, greater thanabout 750, greater than about 1000, or greater than about 2000. Incertain embodiments, the sum of m, n and l disclosed herein is greaterthan about 250, greater than about 300, greater than about 500, greaterthan about 750, greater than about 1000, or greater than about 2000. Insome embodiments, the sum of m, n, l and k disclosed herein is greaterthan about 250, greater than about 300, greater than about 500, greaterthan about 750, greater than about 1000, or greater than about 2000.

In certain embodiments, the number-average molecular weight (M_(n)),weight-average molecular weight (M_(w)), or viscosity-average molecularweight (M_(z)) of the polyfarnesene disclosed herein is greater thanabout 60,000 daltons, greater than about 100,000 daltons, greater than200,000 daltons, greater than 300,000 daltons, greater than about500,000 daltons, greater than 750,000 daltons, greater than 1,000,000daltons, greater than 1,500,000 daltons, or greater than 2,000,000daltons. In other embodiments, the M_(n), M_(w) or M_(z) of thepolyfarnesene disclosed herein is less than about 10,000,000 daltons,less than 5,000,000 daltons, less than 1,000,000 daltons, less thanabout 750,000 daltons, or less than 500,000 daltons.

In some embodiments, the polyfarnesene has at least a glass transitiontemperature (T_(g)) of less than −55° C., less than −60° C., less than−65° C., less than −70° C., or less than −75° C., as measured accordingto ASTM D7426-08 titled “Standard Test Method for Assignment of the DSCProcedure for Determining T _(g) of a Polymer or an ElastomericCompound,” which is incorporated herein by reference.

In some embodiments, the amount of formula (I) is at most about 80 wt.%, based on the total weight of the polyfarnesene. In other embodiments,the sum of m, n and l is greater than about 300. In further embodiments,at least a portion of the double bonds in one or more of formulae (I),(II), (III), (IV), (IX), (XI), (XII) and stereoisomers thereof ishydrogenated.

In some embodiments, the polyfarnesene is a farnesene interpolymer. Infurther embodiments, the farnesene interpolymer disclosed hereincomprises one or more units derived from a farnesene in an amount of atleast about 5 mole percent, at least about 10 mole percent, at leastabout 15 mole percent, at least about 20 mole percent, at least about 30mole percent, at least about 40 mole percent, at least about 50 molepercent, at least about 60 mole percent, at least about 70 mole percent,at least about 80 mole percent, or at least about 90 mole percent of thewhole farnesene interpolymer. In still further embodiments, thefarnesene interpolymer disclosed herein comprises one or more unitsderived from the vinyl monomer in an amount of at least about 5 molepercent, at least about 10 mole percent, at least about 15 mole percent,at least about 20 mole percent, at least about 30 mole percent, at leastabout 40 mole percent, at least about 50 mole percent, at least about 60mole percent, at least about 70 mole percent, at least about 80 molepercent, or at least about 90 mole percent of the whole farneseneinterpolymer.

In certain embodiments, the polyfarnesene comprises one or more polymermolecules having formula (X′):

wherein n is an integer from 1 to about 5,000, from 1 to about 10,000,from 1 to about 50,000, from 1 to about 100,000, from 1 to about200,000, or from 1 to about 500,000; m is an integer from 0 to about5,000, from 0 to about 10,000, from 0 to about 50,000, from 0 to about100,000, from 0 to about 200,000, or from 0 to about 500,000; X isderived from a farnesene; and Y is derived from a vinyl monomer.

In some embodiments, X has one or more of formulae (I′)-(VIII′):

In certain embodiments, Y has formula (IX′):

where R¹, R², R³, R⁴ are as defined herein and each of R⁵, R⁶, R⁷ and R⁸is independently H, an organyl group or a functional group.

In general, the polyfarnesene comprising a mixture of polymer molecules,each of which has formula (X′) wherein each of n and m independently hasa specific value. The average and distribution of the n or m valuesdisclosed herein depend on various factors such as the molar ratio ofthe starting materials, the reaction time and temperature, the presenceor absence of a chain terminating agent, the amount of an initiator ifthere is any, and the polymerization conditions. The farneseneinterpolymer of Formula (X′) may include unreacted comonomers, althoughthe concentrations of the comonomer would generally be small if notextremely small or undetectable. The extent of polymerization, asspecified with n and m values, can affect the properties of theresulting polymer. In some embodiments, n is an integer from 1 to about5,000, from 1 to about 10,000, from 1 to about 50,000, from 1 to about100,000, from 1 to about 200,000, or from 1 to about 500,000; and m isan integer from 0 to about 5,000, from 0 to about 10,000, from 0 toabout 50,000, from 0 to about 100,000, from 0 to about 200,000, or from0 to about 500,000. In other embodiments, n is independently from about1 to about 5000, from about 1 to about 2500, from about 1 to about 1000,from about 1 to about 500, from about 1 to about 100 or from about 1 toabout 50; and m is from about 0 to about 5000, from about 0 to about2500, from about 0 to about 1000, from about 0 to about 500, from about0 to about 100 or from about 0 to about 50. A person of ordinary skillin the art will recognize that additional ranges of average n and mvalues are contemplated and are within the present disclosure.

In some embodiments, formula (X′) comprises two end groups as shown bythe following formula:

where each of the asterisks (*) in the formula represents an end groupwhich may or may not vary between different polymer molecules of thepolyfarnesene depending on many factors such as the molar ratio of thestarting materials, the presence or absence of a chain terminatingagent, and the state of the particular polymerization process at the endof the polymerization step.

In some embodiments, Xs and Ys of formula (X′) are linked in asubstantially linear fashion. In other embodiments, Xs and Ys of formula(X′) are linked in substantially branched fashion. In furtherembodiments, Xs and Ys of formula (X′) are linked in substantiallystar-shaped fashion. In still further embodiments, each of Xs and Ysindependently forms at least a block along the polymer chain so as toprovide a di-block, tri-block or multi-block farnesene interpolymerhaving at least one X block and at least one Y block. In still furtherembodiments, Xs and Ys are randomly distributed along the polymer chainso as to provide a random farnesene interpolymer. In still furtherembodiments, Xs and Ys are alternatively distributed along the polymerchain so as to provide an alternating farnesene interpolymer.

In some embodiments, the amount of the farnesene in the farneseneinterpolymer disclosed herein is greater than about 1.5 mole %, greaterthan about 2.0 mole %, greater than about 2.5 mole %, greater than about5 mole %, greater than about 10 mole %, greater than about 15 mole %, orgreater than about 20 mole %, based on the total amount of the farneseneinterpolymer. In other embodiments, the amount of the farnesene in thefarnesene interpolymer disclosed herein is less than about 90 mole %,less than about 80 mole %, less than about 70 mole %, less than about 60mole %, less than about 50 mole %, less than about 40 mole %, or lessthan about 30 mole %, based on the total amount of the farneseneinterpolymer.

In some embodiments, the amount of the vinyl monomer in the farneseneinterpolymer disclosed herein is greater than about 1.5 mole %, greaterthan about 2.0 mole %, greater than about 2.5 mole %, greater than about5 mole %, greater than about 10 mole %, greater than about 15 mole %, orgreater than about 20 mole %, based on the total amount of the farneseneinterpolymer. In other embodiments, the amount of the vinyl monomer inthe farnesene interpolymer disclosed herein is less than about 90 mole%, less than about 80 mole %, less than about 70 mole %, less than about60 mole %, less than about 50 mole %, less than about 40 mole %, or lessthan about 30 mole %, based on the total amount of the farneseneinterpolymer.

In certain embodiments, the mole percent ratio of the farnesene to thevinyl monomer (i.e., the mole percent ratio of X to Y) in the farneseneinterpolymer disclosed herein is from about 1:5 to about 100:1. In otherembodiments, the mole percent ratio of X to Y is from about 1:4 to about100:1; from about 1:3.5 to about 100:1, from about 1:3 to about 100:1,from about 1:2.5 to about 100:1, or from about 1:2 to about 100:1. Insome embodiments, m is 1 or greater, the mole percent ratio of X to Y isfrom about 1:4 to about 100:1

In certain embodiments, the amount of formula (I′) in the polyfarnesenedisclosed herein is at most about 85 wt. %, at most about 80 wt. %, atmost about 70 wt. %, at most about 60 wt. %, or at most about 50 wt. %,based on the total weight of the polyfarnesene. In other embodiments,the amount of formula (III′) in the polyfarnesene disclosed herein is atleast about 10 wt. %, at least about 15 wt. %, at least about 20 wt. %,at least about 25 wt. %, at least about 30 wt. %, at least about 40 wt.%, at least about 50 wt. %, at least about 60 wt. %, at least about 70wt. %, at least about 75 wt. %, at least about 80 wt. %, at least about85 wt. %, at least about 90 wt. %, at least about 95 wt. %, or at leastabout 99 wt. %, based on the total weight of the polyfarnesene. Infurther embodiments, the amount of formula (II′) in the polyfarnesenedisclosed herein is from about 1 wt. % to about 99 wt. %, from about 5wt. % to about 99 wt. %, from about 10 wt. % to about 99 wt. %, or fromabout 15 wt. % to about 99 wt. %, based on the total weight of thepolyfarnesene. In still further embodiments, the amount of formula (IV′)in the polyfarnesene disclosed herein is at most about 0.1 wt. %, atmost about 0.5 wt. %, at most about 1 wt. %, at most about 2 wt. %, orat most about 3 wt. %, based on the total weight of the polyfarnesene.In some embodiments, the polyfarnesene disclosed herein is substantiallyfree of formula (I′), (II′), (III′) or (IV′).

In certain embodiments, the amount of formula (V′), (VI′), (VII′) or(VIII′) in the polyfarnesene disclosed herein is at most about 1 wt. %,at most about 5 wt. %, at most about 10 wt. %, at most about 20 wt. %,at most about 30 wt. %, at most about 40 wt. %, at most about 50 wt. %,at most about 60 wt. %, at most about 70 wt. %, at most about 80 wt. %,or at most about 90 wt. %, based on the total weight of thepolyfarnesene. In other embodiments, the amount of formula (V′), (VI′),(VII′) or (VIII′) in the polyfarnesene disclosed herein is at leastabout 1 wt. %, at least about 2 wt. %, at least about 3 wt. %, at leastabout 5 wt. %, at least about 10 wt. %, at least about 20 wt. %, atleast about 30 wt. %, at least about 40 wt. %, at least about 50 wt. %,at least about 60 wt. %, based on the total weight of the polyfarnesene.In further embodiments, the amount of formula (V′), (VI′), (VII′) or(VIII′) in the polyfarnesene disclosed herein is from about 1 wt. % toabout 99 wt. %, from about 5 wt. % to about 99 wt. %, from about 10 wt.% to about 99 wt. %, or from about 15 wt. % to about 99 wt. %, based onthe total weight of the polyfarnesene. In some embodiments, thepolyfarnesene disclosed herein is substantially free of formula (V′),(VI′), (VII′) or (VIII′).

Any compound containing a vinyl group, i.e., —CH═CH₂, that iscopolymerizable with farnesene can be used as a vinyl monomer for makingthe farnesene interpolymer disclosed herein. Useful vinyl monomersdisclosed herein include ethylene, i.e., CH₂═CH₂. In certainembodiments, the vinyl monomer has formula (XV):

where each of R⁵, R⁶, R⁷ and R⁸ is independently H, an organyl group ora functional group.

In some embodiments, at least one of R⁵, R⁶, R⁷ and R⁸ of formula (IX),(IX′) or (XV) is an organyl group. In further embodiments, the organylgroup is hydrocarbyl, substituted hydrocarbyl, heterocyclyl orsubstituted heterocyclyl. In certain embodiments, each of R⁵, R⁶, R⁷ andR⁸ of formula (IX), (IX′) or (XV) is independently H, alkyl, cycloalkyl,aryl, alkenyl, cycloalkenyl, alkynyl, heterocyclyl, alkoxy, aryloxy,carboxy, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl,dialkylaminocarbonyl, acyloxy, nitrile or halo. In other embodiments,each of R⁵, R⁶, R⁷ and R⁸ of formula (IX), (IX′) or (XV) isindependently H, alkyl, cycloalkyl, aryl, cycloalkenyl, alkynyl,heterocyclyl, alkoxy, aryloxy, carboxy, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, acyloxy, nitrile or halo. Incertain embodiments, R⁵ of formula (IX), (IX′) or (XV) is aryl; and eachof R⁶, R⁷ and R⁸ is H. In further embodiments, R⁵ of formula (IX), (IX′)or (XV) is phenyl; and each of R⁶, R⁷ and R⁸ is H.

In certain embodiments, at least one of R⁵, R⁶, R⁷ and R⁸ of formula(IX), (IX′) or (XV) is H. In other embodiments, each of R⁵, R⁶, R⁷ andR⁸ of formula (IX), (IX′) or (XV) is H. In further embodiments, R⁵ offormula (IX), (IX′) or (XV) is hydrocarbyl; and each of R⁶, R⁷ and R⁸ isH. In still further embodiments, the hydrocarbyl is alkyl, cycloalkyl oraryl. In still further embodiments, none of R⁵, R⁶, R⁷ and R⁸ of formula(IX), (IX′) or (XV) is or comprises alkenyl, cycloalkenyl or alkynyl. Instill further embodiments, none of R⁵, R⁶, R⁷ and R⁸ of formula (IX),(IX′) or (XV) is or comprises a hydrocarbyl, substituted hydrocarbyl,heterocyclyl or substituted heterocyclyl.

In certain embodiments, at least one of R⁵, R⁶, R⁷ and R⁸ of formula(IX), (IX′) or (XV) is a functional group containing halo, O, N, S, P ora combination thereof. Some non-limiting examples of suitable functionalgroups include hydroxy, alkoxy, aryloxy, amino, nitro, thiol, thioether,imine, cyano, amido, phosphonato (—P(═O)(O-alkyl)₂, —P(═O)(O-aryl)₂, or—P(═O)(O-alkyl))O-aryl), phosphinato (—P(═O)(O-alkyl)alkyl,—P(═O)(O-aryl)alkyl, —P(═O)(O-alkyl)aryl, or —P(═O)(O-aryl)aryl),carboxyl, thiocarbonyl, sulfonyl (—S(═O)₂alkyl, or —S(═O)₂aryl),sulfonamide (—SO₂NH₂, —SO₂NH(alkyl), —SO₂NH(aryl), —SO₂N(alkyl)₂,—SO₂N(aryl)₂, or —SO₂N(aryl)(alkyl)), ketone, aldehyde, ester, oxo,amino (primary, secondary or tertiary), —CO₂CH₃, —CONH₂, —OCH₂CONH₂,—NH₂, —OCHF₂, —OCF₃, —NH(alkyl), —N(alkyl)₂, —NH(aryl), —N(alkyl)(aryl),—N(aryl)₂, —CHO, —CO(alkyl), —CO(aryl), —CO₂(alkyl), or —CO₂(aryl). Insome embodiments, the functional group is or comprises alkoxy, aryloxy,carboxy, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl,dialkylaminocarbonyl, acyloxy, nitrile or halo. In other embodiments,none of R⁵, R⁶, R⁷ and R⁸ of formula (IX), (IX′) or (XV) is or comprisesa functional group. In other embodiments, none of R⁵, R⁶, R⁷ and R⁸ offormula (IX), (IX′) or (XV) is or comprises alkoxy, aryloxy, carboxy,alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl,acyloxy, nitrile or halo.

In some embodiments, the vinyl monomer is a substituted or unsubstitutedolefin such as ethylene or styrene, vinyl halide, vinyl ether,acrylonitrile, acrylic ester, methacrylic ester, acrylamide,methacrylamide or a combination thereof. In other embodiments, the vinylmonomer is ethylene, an α-olefin or a combination thereof. Somenon-limiting examples of suitable α-olefins include styrene, propylene,1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene,1,5-hexadiene and combinations thereof.

In some embodiments, the vinyl monomer is an aryl such as styrene,α-methyl styrene, or di-vinyl benzene. Additional examples include thefunctionalized vinyl aryls such as those disclosed by U.S. Pat. No.7,041,761 which is incorporated herein by reference.

In some embodiments, the farnesene interpolymers disclosed herein arederived from at least one farnesene and at least one olefin monomer. Anolefin refers to an unsaturated hydrocarbon-based compound with at leastone carbon-carbon double bond. In certain embodiments, the olefin is aconjugated diene. Depending on the selection of catalysts, any olefinmay be used in embodiments of the invention. Some non-limiting examplesof suitable olefins include C₂₋₂₀ aliphatic and C₈₋₂₀ aromatic compoundscontaining vinylic unsaturation, as well as cyclic compounds, such ascyclobutene, cyclopentene, dicyclopentadiene, and norbornene, includingbut not limited to, norbornene substituted in the 5 and 6 position withC₁₋₂₀ hydrocarbyl or cyclohydrocarbyl groups. Other non-limitingexamples of suitable olefins include mixtures of such olefins as well asmixtures of such olefins with C₄₋₄₀ diolefin compounds.

Some non-limiting examples of suitable olefin or α-olefin monomersinclude styrene, ethylene, propylene, isobutylene, 1-butene, 1-pentene,1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene,3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene,4,6-dimethyl-1-heptene, 4-vinylcyclohexene, vinylcyclohexane,norbornadiene, ethylidene norbornene, cyclopentene, cyclohexene,dicyclopentadiene, cyclooctene, C₄₋₄₀ dienes, including but not limitedto 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene, 1,5-hexadiene,1,7-octadiene, 1,9-decadiene, other C₄₋₄₀ α-olefins, and the like. Incertain embodiments, the olefin monomer is propylene, 1-butene,1-pentene, 1-hexene, 1-octene or a combination thereof.

The farnesene interpolymers disclosed herein may derived from afarnesene and styrene. The farnesene interpolymers may further compriseat least one C₂₋₂₀ olefin, at least one C₄₋₁₈ diolefin, at least onealkenylbenzene or a combination thereof. Suitable unsaturated comonomersuseful for polymerizing with farnesene include, for example,ethylenically unsaturated monomers, polyenes such as conjugated ornonconjugated dienes, alkenylbenzenes, and the like. Examples of suchcomonomers include ethylene, C₂₋₂₀ olefins such as propylene,isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene,1-heptene, 1-octene, 1-nonene, 1-decene, and the like. Other suitablemonomers include styrene, halo- or alkyl-substituted styrenes,vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene, and cycloalkenessuch as cyclopentene, cyclohexene and cyclooctene.

Some suitable non-conjugated diene monomers can be a straight chain,branched chain or cyclic hydrocarbon diene having from 6 to 15 carbonatoms. Some non-limiting examples of suitable non-conjugated dienesinclude straight chain acyclic dienes, such as 1,4-hexadiene,1,6-octadiene, 1,7-octadiene, 1,9-decadiene, branched chain acyclicdienes, such as 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene;3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyricene anddihydroocinene, single ring alicyclic dienes, such as1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and1,5-cyclododecadiene, and multi-ring alicyclic fused and bridged ringdienes, such as tetrahydroindene, methyl tetrahydroindene,dicyclopentadiene, bicyclo-(2,2,1)-hepta-2,5-diene; alkenyl, alkylidene,cycloalkenyl and cycloalkylidene norbornenes, such as5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene,5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene,5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and norbornadiene.Of the dienes typically used to prepare EPDMs, the particularlypreferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene(ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB),and dicyclopentadiene (DCPD). In certain embodiments, the diene is5-ethylidene-2-norbornene (ENB) or 1,4-hexadiene (HD). In otherembodiments, the farnesene interpolymers are not derived from a polyenesuch as dienes, trienes, tetraenes and the like.

In some embodiments, the farnesene interpolymers are interpolymers offarnesene, styrene, and a C₂₋₂₀ olefin. Some non-limiting examples ofsuitable olefins include ethylene, propylene, isobutylene, 1-butene,1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene. In someembodiments, the farnesene interpolymers disclosed herein are notderived from ethylene. In some embodiments, the farnesene interpolymersdisclosed herein are not derived from one or more C₂₋₂₀ olefins.

In certain embodiments, the vinyl monomer does not comprise a terpene.In other embodiments, the vinyl monomer does not comprise a terpeneselected from isoprene, dipentene, α-pinene, β-pinene, terpinolene,limonene (dipentene), terpinene, thujene, sabinene, 3-carene, camphene,cadinene, caryophyllene, myrcene, ocimene, cedrene, bisalbone,bisalbone, bisalbone, zingiberene, humulene, citronellol, linalool,geraniol, nerol, ipsenol, terpineol, D-terpineol-(4), dihydrocarveol,nerolidol, farnesol, eudesmol, citral, D-citronellal, carvone,D-pulegone, piperitone, carvenone, bisabolene, selinene, santalene,vitamin A, abietic acid or a combination thereof. In furtherembodiments, the vinyl monomer does not comprise an isoprene.

The farnesene interpolymers can be functionalized by incorporating atleast one functional group in their polymer structure. Exemplaryfunctional groups may include, for example, ethylenically unsaturatedmono- and di-functional carboxylic acids, ethylenically unsaturatedmono- and di-functional carboxylic acid anhydrides, salts thereof andesters thereof. Such functional groups may be grafted to the farneseneinterpolymers, or they may be copolymerized farnesene with an optionaladditional comonomer to form an interpolymer of farnesene, thefunctional comonomer and optionally other comonomer(s). Any means forgrafting functional groups known to a skilled artisan can be used. Oneparticularly useful functional group is maleic anhydride.

The amount of the functional group present in the functionalizedfarnesene interpolymer may vary. In some embodiments, the functionalgroup is present in an amount of at least about 1.0 wt. %, at leastabout 2.5 wt. %, at least about 5 wt. %, at least about 7.5 wt. %, or atleast about 10 wt. %, based on the total weight of the farneseneinterpolymer. In other embodiments, the functional group is present inan amount of less than about 40 wt. %, less than about 30 wt. %, lessthan about 25 wt. %, less than about 20 wt. %, or less than about 15 wt.%, based on the total weight of the farnesene interpolymer.

Any catalyst that can polymerize or copolymerize farnesene can be usedfor making the polyfarnesenes disclosed herein. Some non-limitingexamples of suitable catalysts include organolithium reagents,Ziegler-Natta catalysts, Kaminsky catalysts and other metallocenecatalysts. In some embodiments, the catalyst is a Ziegler-Nattacatalyst, a Kaminsky catalyst, a metallocene catalyst or a combinationthereof.

In some embodiments, the catalyst further comprises a cocatalyst. Infurther embodiments, the cocatalyst is a hydride, alkyl or aryl of ametal or a combination thereof. In still further embodiments, the metalis aluminum, lithium, zinc, tin, cadmium, beryllium or magnesium.

In some embodiments, the catalyst is an organolithium reagent. Anyorganolithium reagent that can act as a catalyst to polymerize olefinscan be used herein. Some non-limiting examples of suitable organolithiumreagents include n-butyllithium, sec-butyllithium or tert-butyllithium.Some non-limiting examples of suitable Lewis bases include TMEDA, PMDTAor sparteine. Some organolithium reagents are disclosed in Zvi Rappoportet al., “The Chemistry of Organolithium Compounds,” Part 1 (2004) andVol. 2 (2006), both of which are incorporated herein by reference.

In some embodiments, the catalyst is a mixture of an organolithiumreagent and a Lewis base. Any Lewis base that can deaggregateorganolithium reagents, making them more soluble and more reactive, canbe used herein. An aggregated organolithium reagent generally has onelithium coordinating to more than one carbon atom and one carboncoordinating to more than one lithium atom. Some non-limiting examplesof suitable Lewis bases include 1,2-bis(dimethylamino)ethane (also knownas tetramethylethylenediamine or TMEDA),N,N,N′,N′,N″-pentamethyldiethylenetriamine (PMDTA), sparteine andcombinations thereof.

In some embodiments, the catalyst is a Ziegler-Natta catalyst.Generally, Ziegler-Natta catalysts can be heterogeneous or homogeneous.In some embodiments, the Ziegler-Natta catalyst used for polymerizingthe polyfarnesenes disclosed herein is a heterogeneous Ziegler-Nattacatalyst. Some useful Ziegler-Natta catalysts are disclosed in J. Boor,“Ziegler-Natta Catalysts and Polymerizations,” Saunders CollegePublishing, pp. 1-687 (1979); and Malcolm P. Stevens, “PolymerChemistry, an Introduction,” Third Edition, Oxford University Press, pp.236-245 (1999), both of which are incorporated herein by reference.

Heterogeneous Ziegler-Natta catalysts generally comprise (1) atransition metal compound comprising an element from groups IV to VIII;and (2) an organometallic compound comprising a metal from groups I toIII of the periodic table. The transition metal compound is referred asthe catalyst while the organometallic compound is regarded as thecocatalyst or activator. The transition metal compound generallycomprises a metal and one or more anions and ligands. Some non-limitingexamples of suitable metals include titanium, vanadium, chromium,molybdenum, zirconium, iron and cobalt. Some non-limiting examples ofsuitable anions or ligands include halides, oxyhalides, alkoxy,acetylacetonyl, cyclopentadienyl, and phenyl.

Any cocatalyst or activator that can ionize the organometallic complexto produce an active olefin polymerization catalyst can be used herein.Generally, the organometallic cocatalysts are hydrides, alkyls, or arylsof metals, such as aluminum, lithium, zinc, tin, cadmium, beryllium, andmagnesium. Some non-limiting examples of suitable cocatalysts includealumoxanes (methyl alumoxane (MAO), PMAO, ethyl alumoxane, diisobutylalumoxane), alkylaluminum compounds (trimethylaluminum,triethylaluminum, diethyl aluminum chloride, trimethylaluminum,triisobutylaluminum, trioctylaluminum), diethylzinc, di(i-butyl)zinc,di(n-hexyl)zinc, and ethylzinc (t-butoxide) and the like. Other suitablecocatalysts include acid salts that contain non-nucleophilic anions.These compounds generally consist of bulky ligands attached to boron oraluminum. Some non-limiting examples of such compounds include lithiumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)aluminate, aniliniumtetrakis(pentafluorophenyl)borate, and the like. Some non-limitingexamples of suitable cocatalysts also include organoboranes, whichinclude boron and one or more alkyl, aryl, or aralkyl groups. Othernon-limiting examples of suitable cocatalysts include substituted andunsubstituted trialkyl and triarylboranes such astris(pentafluorophenyl)borane, triphenylborane, tri-n-octylborane, andthe like. These and other suitable boron-containing cocatalysts oractivators are described in U.S. Pat. Nos. 5,153,157, 5,198,401, and5,241,025, both of which are incorporated herein by reference.

In certain embodiments, the Ziegler-Natta catalyst can be impregnated ona support material. Some suitable support materials are disclosed inMalcolm P. Stevens, “Polymer Chemistry, an Introduction,” Third Edition,Oxford University Press, p. 251 (1999), which is incorporated herein byreference.

The support material is generally a material inert or substantiallyinert to olefin polymerization reactions. Non-limiting examples ofsuitable support materials include MgCl₂, MgO, alumina such as activatedalumina and microgel alumina, silica, magnesia, kieselguhr, fuller'searth, clays, alumina silicates, porous rare earth halides andoxylalides, and combinations thereof. The support material can have asurface area between about 5 m²/g and about 450 m²/g, as determined bythe BET (Brunauer-Emmet-Teller) method of measuring surface area, asdescribed by S. Brunauer, P. H. Emmett, and E. Teller, Journal of theAmerican Chemical Society, 60, 309 (1938), which is incorporated hereinby reference. In some embodiments, the surface area of the supportmaterial is between about 10 m²/g and about 350 m²/g. In furtherembodiments, the surface area of the support material is between about25 m²/g and about 300 m²/g.

The support material can have an average particle size ranging fromabout 20 to about 300 microns, from about 20 to about 250 microns, fromabout 20 to about 200 microns, from about 20 to about 150 microns, fromabout 20 to about 120 microns, from about 30 to about 100 microns, orfrom about 30 to about 90 microns. The compacted or tamped bulk densityof the support material can vary between about 0.6 and about 1.6 g/cc,between about 0.7 and about 1.5 g/cc, between about 0.8 and about 1.4g/cc, or between about 0.9 and about 1.3 g/cc.

In certain embodiments, the catalyst used herein is or comprises aKaminsky catalyst, also known as homogeneous Ziegler-Natta catalyst. TheKaminsky catalyst can be used to produce polyolefins such as thepolyfarnesenes disclosed herein with unique structures and physicalproperties. Some Kaminsky catalysts or homogeneous Ziegler-Nattacatalysts are disclosed in Malcolm P. Stevens, “Polymer Chemistry, anIntroduction,” Third Edition, Oxford University Press, pp. 245-251(1999); and John Scheirs and Walter Kaminsky, “Metallocene-BasedPolyolefins: Preparation, Properties, and Technology,” Volume 1, Wiley(2000), both of which are incorporated herein by reference.

In some embodiments, the Kaminsky catalyst suitable for making thepolyfarnesene disclosed herein comprises a transition-metal atomsandwiched between ferrocene ring structures. In other embodiments, theKaminsky catalyst can be represented by the formula Cp₂MX₂, where M is atransition metal (e.g., Zr, Ti or Hf); X is halogen (e.g., Cl), alkyl ora combination thereof; and Cp is a ferrocenyl group. In furtherembodiments, the Kaminsky catalyst has formula (XVI):

wherein Z is an optional divalent bridging group, usually C(CH₃)₂,Si(CH₃)₂, or CH₂CH₂; R is H or alkyl; M is a transition metal (e.g., Zr,Ti or Hf); X is halogen (e.g., Cl), alkyl or a combination thereof. Somenon-limiting examples of Kaminsky catalysts have formulae (XVII) to(XIX):

wherein M is Zr, Hf or Ti.

In some embodiments, a cocatalyst is used with the Kaminsky catalyst.The cocatalyst may be any of the cocatalyst disclosed herein. In certainembodiments, the cocatalyst is methylaluminoxane (MAO). MAO is anoligomeric compound having a general formula (CH₃AlO)_(n), where n isfrom 1 to 10. MAO may play several roles: it alkylates the metalloceneprecursor by replacing chlorine atoms with methyl groups; it producesthe catalytic active ion pair Cp₂MCH₃ ⁺/MAO⁻, where the cationic moietyis considered responsible for polymerization and MAO⁻ acts as weaklycoordinating anion. Some non-limiting examples of MAO include formulae(XX) to (XXI):

In certain embodiments, the catalyst for making the farneseneinterpolymer disclosed herein is or comprises a metallocene catalyst.Some metallocene catalysts are disclosed in Tae Oan Ahn et al.,“Modification of a Ziegler-Natta catalyst with a metallocene catalystand its olefin polymerization behavior,” Polymer Engineering andScience, 39(7), p. 1257 (1999); and John Scheirs and Walter Kaminsky,“Metallocene-Based Polyolefins: Preparation, Properties, andTechnology,” Volume 1, Wiley (2000), both of which are incorporatedherein by reference.

In other embodiments, the metallocene catalyst comprises complexes witha transition metal centre comprising a transition metal, such as Ni andPd, and bulky, neutral ligands comprising alpha-diimine or diketimine.In further embodiments, the metallocene catalyst has formula (XXII):

wherein M is Ni or Pd.

In some embodiments, the catalyst used herein is or comprises ametallocene catalyst bearing mono-anionic bidentate ligands. Anon-limiting example of such a metallocene catalyst has structure(XXIII):

In other embodiments, the catalyst used herein is or comprises ametallocene catalyst comprising iron and a pyridyl is incorporatedbetween two imine groups giving a tridentate ligand. A non-limitingexample of such a metallocene catalyst has structure (XXIV):

In some embodiments, the catalyst used herein is or comprises ametallocene catalyst comprising a salicylamine catalyst system based onzirconium. A non-limiting example of such a metallocene catalyst hasstructure (XXV):

In some embodiments, the farnesene homopolymer disclosed herein isprepared by a process comprising the steps of:

(a) making a farnesene from a simple sugar or non-fermentable carbonsource by using a microorganism; and

(b) polymerizing the farnesene in the presence of a catalyst disclosedherein.

In certain embodiments, the farnesene interpolymer disclosed herein isprepared by a process comprising the steps of:

(a) making a farnesene from a simple sugar or non-fermentable carbonsource by using a microorganism; and

(b) copolymerizing the farnesene and at least one vinyl monomer in thepresence of a catalyst disclosed herein.

In some embodiments, the polyfarnesene disclosed herein is prepared bypolymerizing a β-farnesene in the presence of a catalyst, wherein theamount of the cis-1,4-microstructure in the polyfarnesene is at mostabout 80 wt. %, at most about 75 wt. %, at most about 70 wt. %, at mostabout 65 wt. %, or at most about 60 wt. %, based on the total weight ofthe polyfarnesene. In some embodiments, the β-farnesene is copolymerizedwith a vinyl monomer to form a farnesene copolymer. In otherembodiments, the vinyl monomer is styrene. In further embodiments, thefarnesene copolymer is a block copolymer.

In certain embodiments, the polyfarnesene disclosed herein is preparedby polymerizing an α-farnesene in the presence of a catalyst, whereinthe amount of the cis-1,4-microstructure in the polyfarnesene is fromabout 1 wt. % to about 99 wt. %, from about 10 wt. % to about 99 wt. %,from about 20 wt. % to about 99 wt. %, from about 30 wt. % to about 99wt. %, from about 40 wt. % to about 99 wt. %, from about 50 wt. % toabout 99 wt. %, from about 1 wt. % to about 99 wt. %, from about 1 wt. %to about 90 wt. %, from about 1 wt. % to about 80 wt. %, from about 1wt. % to about 70 wt. %, or from about 1 wt. % to about 60 wt. %, basedon the total weight of the polyfarnesene. In some embodiments, theα-farnesene is copolymerized with a vinyl monomer to form a farnesenecopolymer. In other embodiments, the vinyl monomer is styrene. Infurther embodiments, the farnesene copolymer is a block copolymer.

In some embodiments, the polyfarnesene disclosed herein can behydrogenated partially or completely by any hydrogenating agent known toa skilled artisan. For example, a saturated polyfarnesene can beprepared by (a) polymerizing a farnesene disclosed herein in thepresence of a catalyst disclosed herein to form a polyfarnesene; and (b)hydrogenating at least a portion of the double bonds in thepolyfarnesene in the presence of a hydrogenation reagent. In someembodiments, the farnesene is copolymerized with a vinyl monomerdisclosed herein to form a farnesene copolymer. In other embodiments,the vinyl monomer is styrene. In further embodiments, the farnesenecopolymer is a block copolymer. In still further embodiments, thefarnesene is α-farnesene or β-farnesene or a combination thereof.

In certain embodiments, the hydrogenation reagent is hydrogen in thepresence of a hydrogenation catalyst. In some embodiments, thehydrogenation catalyst is Pd, Pd/C, Pt, PtO₂, Ru(PPh₃)₂Cl₂, Raney nickelor a combination thereof. In one embodiment, the catalyst is a Pdcatalyst. In another embodiment, the catalyst is 5% Pd/C. In a furtherembodiment, the catalyst is 10% Pd/C in a high pressure reaction vesseland the hydrogenation reaction is allowed to proceed until completion.Generally, after completion, the reaction mixture can be washed,concentrated, and dried to yield the corresponding hydrogenated product.Alternatively, any reducing agent that can reduce a C═C bond to a C—Cbond can also be used. For example, the polyfarnesene can behydrogenated by treatment with hydrazine in the presence of a catalyst,such as 5-ethyl-3-methyllumiflavinium perchlorate, under an oxygenatmosphere to give the corresponding hydrogenated products. Thereduction reaction with hydrazine is disclosed in Imada et al., J. Am.Chem. Soc., 127, 14544-14545 (2005), which is incorporated herein byreference.

In some embodiments, at least a portion of the C═C bonds of thepolyfarnesene disclosed herein is reduced to the corresponding C—C bondsby hydrogenation in the presence of a catalyst and hydrogen at roomtemperature. In other embodiments, at least a portion of the C═C bondsof one or more of formulae (I′)-(III′), (V′)-(VII′), and (XI)-(XIV) andstereoisomers thereof is reduced to the corresponding C—C bonds byhydrogenation in the presence of a catalyst and hydrogen at roomtemperature. In further embodiments, the hydrogenation catalyst is 10%Pd/C.

In certain embodiments, the vinyl monomer is styrene. In someembodiments, the farnesene is α-farnesene or β-farnesene or acombination thereof. In other embodiments, the farnesene is prepared byusing a microorganism. In further embodiments, the farnesene is derivedfrom a simple sugar or non-fermentable carbon source.

Farnesene

The farnesene can be derived from any source or prepared by any methodknown to a skilled artisan. In some embodiments, the farnesene isderived from a chemical source (e.g., petroleum or coal) or obtained bya chemical synthetic method. In other embodiments, the farnesene isprepared by fractional distillation of petroleum or coal tar. In furtherembodiments, the farnesene is prepared by any known chemical syntheticmethod. One non-limiting example of suitable chemical synthetic methodincludes dehydrating nerolidol with phosphoryl chloride in pyridine asdescribed in the article by Anet E. F. L. J., “Synthesis of(E,Z)-α-,(Z,Z)-α-, and (Z)-β-farnesene,” Aust. J. Chem., 23(10),2101-2108 (1970), which is incorporated herein by reference.

In some embodiments, the farnesene can be obtained or derived fromnaturally occurring terpenes that can be produced by a wide variety ofplants, such as Copaifera langsdorfii, conifers, and spurges; insects,such as swallowtail butterflies, leaf beetles, termites, and pinesawflies; and marine organisms, such as algae, sponges, corals,mollusks, and fish.

Copaifera langsdorfii or Copaifera tree is also known as the diesel treeand kerosene tree. It has many names in local languages, includingkupa'y, cabismo, and copaúva. Copaifera tree may produce a large amountof terpene hydrocarbons in its wood and leaves. Generally, one Copaiferatree can produce from about 30 to about 40 liters of terpene oil peryear.

Terpene oils can also be obtained from conifers and spurges. Conifersbelong to the plant division Pinophyta or Coniferae and are generallycone-bearing seed plants with vascular tissue. The majority of conifersare trees, but some conifers can be shrubs. Some non-limiting examplesof suitable conifers include cedars, cypresses, douglas-firs, firs,junipers, kauris, larches, pines, redwoods, spruces, and yews. Spurges,also known as Euphorbia, are a very diverse worldwide genus of plants,belonging to the spurge family (Euphorbiaceae). Consisting of about 2160species, spurges are one of the largest genera in the plant kingdom.

The farnesene is a sesquiterpene which are part of a larger class ofcompound called terpenes. A large and varied class of hydrocarbons,terpenes include hemiterpenes, monoterpenes, sesquiterpenes, diterpenes,sesterterpenes, triterpenes, tetraterpenes, and polyterpenes. As aresult, the farnesene can be isolated or derived from terpene oils foruse in the present invention.

In certain embodiments, the farnesene is derived from a biologicalsource. In other embodiments, the farnesene can be obtained from areadily available, renewable carbon source. In further embodiments, thefarnesene is prepared by contacting a cell capable of making a farnesenewith a carbon source under conditions suitable for making the farnesene.

Any carbon source that can be converted into one or more isoprenoidcompounds can be used herein. In some embodiments, the carbon source isa sugar or a non-fermentable carbon source. The sugar can be any sugarknown to those of skill in the art. In certain embodiments, the sugar isa monosaccharide, disaccharide, polysaccharide or a combination thereof.In other embodiments, the sugar is a simple sugar (a monosaccharide or adisaccharide). Some non-limiting examples of suitable monosaccharidesinclude glucose, galactose, mannose, fructose, ribose and combinationsthereof. Some non-limiting examples of suitable disaccharides includesucrose, lactose, maltose, trehalose, cellobiose and combinationsthereof. In still other embodiments, the simple sugar is sucrose. Incertain embodiments, the bioengineered fuel component can be obtainedfrom a polysaccharide. Some non-limiting examples of suitablepolysaccharides include starch, glycogen, cellulose, chitin andcombinations thereof.

The sugar suitable for making the farnesene can be found in a widevariety of crops or sources. Some non-limiting examples of suitablecrops or sources include sugar cane, bagasse, miscanthus, sugar beet,sorghum, grain sorghum, switchgrass, barley, hemp, kenaf, potatoes,sweet potatoes, cassava, sunflower, fruit, molasses, whey or skim milk,corn, stover, grain, wheat, wood, paper, straw, cotton, many types ofcellulose waste, and other biomass. In certain embodiments, the suitablecrops or sources include sugar cane, sugar beet and corn. In otherembodiments, the sugar source is cane juice or molasses.

A non-fermentable carbon source is a carbon source that cannot beconverted by the organism into ethanol. Some non-limiting examples ofsuitable non-fermentable carbon sources include acetate and glycerol.

In certain embodiments, the farnesene can be prepared in a facilitycapable of biological manufacture of C₁₅ isoprenoids. The facility cancomprise any structure useful for preparing the C₁₅ isoprenoids, such asα-farnesene, β-farnesene, nerolidol or farnesol, using a microorganism.In some embodiments, the biological facility comprises one or more ofthe cells disclosed herein. In other embodiments, the biologicalfacility comprises a cell culture comprising at least a C₁₅ isoprenoidin an amount of at least about 1 wt. %, at least about 5 wt. %, at leastabout 10 wt. %, at least about 20 wt. %, or at least about 30 wt. %,based on the total weight of the cell culture. In further embodiments,the biological facility comprises a fermentor comprising one or morecells described herein.

Any fermentor that can provide cells or bacteria a stable and optimalenvironment in which they can grow or reproduce can be used herein. Insome embodiments, the fermentor comprises a culture comprising one ormore of the cells disclosed herein. In other embodiments, the fermentorcomprises a cell culture capable of biologically manufacturing farnesylpyrophosphate (FPP). In further embodiments, the fermentor comprises acell culture capable of biologically manufacturing isopentenyldiphosphate (IPP). In certain embodiments, the fermentor comprises acell culture comprising at least a C₁₅ isoprenoid in an amount of atleast about 1 wt. %, at least about 5 wt. %, at least about 10 wt. %, atleast about 20 wt. %, or at least about 30 wt. %, based on the totalweight of the cell culture.

The facility can further comprise any structure capable of manufacturingthe fuel component or fuel additive from the C₁₅ isoprenoid, such asα-farnesene, β-farnesene, nerolidol or farnesol. The structure maycomprise a reactor for dehydrating the nerolidol or farnesol toα-farnesene or β-farnesene. Any reactor that can be used to convert analcohol into an alkene under conditions known to skilled artisans may beused herein. The reactor may comprise a dehydrating catalyst disclosedherein. In some embodiments, the structure further comprises a mixer, acontainer, and a mixture of the dehydrating products from thedehydrating step.

The biosynthetic process of making C₁₅ isoprenoid compounds aredisclosed in U.S. Pat. No. 7,399,323; U.S. Application Number US2008/0274523; and PCT Publication Numbers WO 2007/140339 and WO2007/139924, which are incorporated herein by reference.

α-Farnesene

α-Farnesene, whose structure is

is found in various biological sources including, but not limited to,the Dufour's gland in ants and in the coating of apple and pear peels.Biochemically, α-farnesene is made from FPP by α-farnesene synthase.Some non-limiting examples of suitable nucleotide sequences that encodesuch an enzyme include (DQ309034; Pyrus communis cultivar d'Anjou) and(AY182241; Malus domestica). See Pechouus et al., Planta 219(1):84-94(2004).β-Farnesene

β-Farnesene, whose structure is

is found in various biological sources including, but not limited to,aphids and essential oils such as peppermint oil. In some plants such aswild potato, β-farnesene is synthesized as a natural insect repellent.Biochemically, β-farnesene is made from FPP by β-farnesene synthase.Some non-limiting examples of suitable nucleotide sequences that encodesuch an enzyme include (AF024615; Mentha×piperita) and (AY835398;Artemisia annua). See Picaud et al., Phytochemistry 66(9): 961-967(2005).Farnesol

Farnesol, whose structure is

is found in various biological sources including insects and essentialoils from cintronella, neroli, cyclamen, lemon grass, tuberose, androse. Biochemically, farnesol is made from FPP by a hydroxylase such asfarnesol synthase. Some non-limiting examples of suitable nucleotidesequences that encode such an enzyme include (AF529266; Zea mays) and(YDR481C; Saccharomyces cerevisiae). See Song, L., Applied Biochemistryand Biotechnology 128:149-158 (2006).Nerolidol

Nerolidol, whose structure is

is also known as peruviol which is found in various biological sourcesincluding essential oils from neroli, ginger, jasmine, lavender, teatree, and lemon grass. Biochemically, nerolidol is made from FPP by ahydroxylase such as nerolidol synthase. A non-limiting example of asuitable nucleotide sequence that encodes such an enzyme includesAF529266 from Zea mays (maize; gene tps1).

The farnesol and nerolidol disclosed herein may be converted intoα-farnesene, β-farnesene or a combination thereof by dehydration with adehydrating agent or an acid catalyst. Any dehydrating agent or an acidcatalyst that can convert an alcohol into an alkene can be used herein.Some non-limiting examples of suitable dehydrating agents or acidcatalysts include phosphoryl chloride, anhydrous zinc chloride,phosphoric acid and sulfuric acid.

General Procedures of Making Polyfarnesenes

The polymerization of a farnesene or the copolymerization of a farnesenewith a vinyl comonomer can be performed over a wide temperature range.In certain embodiments, the polymerization temperature is from about−30° C. to about 280° C., from about 30° C. to about 180° C., or fromabout 60° C. to about 100° C. The partial pressures of the vinylcomonomers can range from about 15 psig (0.1 MPa) to about 50,000 psig(245 MPa), from about 15 psig (0.1 MPa) to about 25,000 psig (172.5MPa), from about 15 psig (0.1 MPa) to about 10,000 psig (69 MPa), fromabout 15 psig (0.1 MPa) to about 5,000 psig (34.5 MPa) or from about 15psig (0.1 MPa) to about 1,000 psig (6.9 MPa).

The concentration of the catalyst used for making the polyfarnesenesdisclosed herein depends on many factors. In some embodiment, theconcentration ranges from about 0.01 micromoles per liter to about 100micromoles per liter. The polymerization time depends on the type ofprocess, the catalyst concentration, and other factors. Generally, thepolymerization time is within several minutes to several hours.

A non-limiting example of solution polymerization procedure forfarnesene homopolymer is outlined below. A farnesene such as β-farnesenecan be added to a solvent such as cyclohexane to form a solution in areactor which may be optionally under a nitrogen or argon atmosphere.The solution can be dried over a drying agent such as molecular sieves.A catalyst such as organolithium reagent can be added into the reactor,and then the reactor is heated to an elevated temperature until all or asubstantial portion of farnesene is consumed. The farnesene homopolymercan then be precipitated from the reaction mixture and dried in a vacuumoven.

A non-limiting example of solution polymerization procedure forfarnesene interpolymer is outlined below. A farnesene such asβ-farnesene can be added to a solvent such as cyclohexane to form afarnesene solution in a reactor optionally under a nitrogen or argonatmosphere. The farnesene solution can be dried over a drying agent suchas molecular sieves. In a second reactor optionally under nitrogen orargon atmosphere, a solution of styrene in cyclohexane with 10% issimilarly prepared and dried over a drying agent such as molecularsieves. The styrene is polymerized by a catalyst such as organolithiumreagent at an elevated temperature until all or a substantial portion ofstyrene is consumed. Then, the farnesene solution is transferred to thesecond reactor. The reaction is allowed to react until all or asubstantial portion of farnesene is consumed. Then a dichlorosilanecoupling agent (e.g., dichlorodimethylsilane in 1,2-dichloroethane) isthen added into the second reactor to form a farnesene interpolymer.

Polyfarnesene Compositions

The polyfarnesenes can be used to prepare polyfarnesene compositions fora wide variety of applications. In some embodiments, the polyfarnesenecompositions comprise the polyfarnesene disclosed herein and a secondpolymer or at least an additive. In certain embodiments, thepolyfarnesene compositions comprise a second polymer. In otherembodiments, the polyfarnesene compositions do not comprise a secondpolymer. The second polymer can be a vinyl polymer or polyfarnesene, anon-vinyl polymer or polyfarnesene, or a combination thereof. Somenon-limiting examples of vinyl polymers and polyfarnesenes are disclosedin Malcolm P. Stevens, “Polymer Chemistry, an Introduction,” ThirdEdition, Oxford University Press, pp. 17-21 and 167-279 (1999), which isincorporated herein by reference. Some non-limiting examples of suitablesecond polymer include a polyolefin, polyurethane, polyester, polyamide,styrenic polymer, phenolic resin, polyacrylate, polymethacrylate or acombination thereof.

In certain embodiments, the ratio of the polyfarnesene to the secondpolymer is from about 1:99 to about 99:1, from about 1:50 to about 50:1,from about 1:25 to about 25:1 or from about 1:10 to about 10:1.

In some embodiments, the second polymer is a polyolefin (e.g.,polyethylene, polypropylene, an ethylene/α-olefin interpolymer, acopolymer of ethylene and propylene, and a copolymer of ethylene andvinyl acetate (EVA)), polyurethane, polyester, polyamide, styrenicpolymer (e.g., polystyrene, poly(acrylonitrile-butadiene-styrene),poly(styrene-butadiene-styrene) and the like), phenolic resin,polyacrylate, polymethacrylate or a combination thereof. In someembodiments, the second polymer is polyethylene, polypropylene,polystyrene, a copolymer of ethylene and vinyl acetate,poly(acrylonitrile-butadiene-styrene), poly(styrene-butadiene-styrene)or a combination thereof. The second polymer may be blended with thefarnesene interpolymer before it is added to the polyfarnesenecomposition. In some embodiments, the second polymer is added directlyto the polyfarnesene composition without pre-blending with the farneseneinterpolymer.

The weight ratio of the polyfarnesene to the second polymer in thepolymer composition can be between about 1:99 and about 99:1, betweenabout 1:50 and about 50:1, between about 1:25 and about 25:1, betweenabout 1:10 and about 10:1, between about 1:9 and about 9:1, betweenabout 1:8 and about 8:1, between about 1:7 and about 7:1, between about1:6 and about 6:1, between about 1:5 and about 5:1, between about 1:4and about 4:1, between about 1:3 and about 3:1, between about 1:2 andabout 2:1, between about 3:7 and about 7:3 or between about 2:3 andabout 3:2.

In some embodiments, the second polymer is a polyolefin. Any polyolefinthat is partially or totally compatible with the polyfarnesene may beused. Non-limiting examples of suitable polyolefins includepolyethylenes; polypropylenes; polybutylenes (e.g., polybutene-1);polypentene-1; polyhexene-1; polyoctene-1; polydecene-1;poly-3-methylbutene-1; poly-4-methylpentene-1; polyisoprene;polybutadiene; poly-1,5-hexadiene; interpolymers derived from olefins;interpolymers derived from olefins and other polymers such as polyvinylchloride, polystyrene, polyurethane, and the like; and mixtures thereof.In some embodiments, the polyolefin is a homopolymer such aspolyethylene, polypropylene, polybutylene, polypentene-1,poly-3-methylbutene-1, poly-4-methylpentene-1, polyisoprene,polybutadiene, poly-1,5-hexadiene, polyhexene-1, polyoctene-1 andpolydecene-1.

Some non-limiting examples of suitable polyethylenes include ultra lowdensity polyethylene (ULDPE), linear low density polyethylene (LLDPE),low density polyethylene (LDPE), medium density polyethylene (MDPE),high density polyethylene (HDPE), high molecular weight high densitypolyethylene (HMW-HDPE), ultra high molecular weight polyethylene(UHMW-PE) and combinations thereof. Some non-limiting examples ofpolypropylenes include low density polypropylene (LDPP), high densitypolypropylene (HDPP), high-melt strength polypropylene (HMS-PP) andcombination thereof. In some embodiments, the second polymer is orcomprises high-melt-strength polypropylene (HMS-PP), low densitypolyethylene (LDPE) or a combination thereof.

In some embodiments, the polyfarnesene compositions disclosed hereincomprise at least one additive for the purposes of improving and/orcontrolling the processability, appearance, physical, chemical, and/ormechanical properties of the polyfarnesene compositions. In someembodiments, the polyfarnesene compositions do not comprise an additive.Any plastics additive known to a person of ordinary skill in the art maybe used in the polyfarnesene compositions disclosed herein. Non-limitingexamples of suitable additives include fillers, grafting initiators,tackifiers, slip agents, anti-blocking agents, plasticizers,antioxidants, blowing agents, blowing agent activators (e.g., zincoxide, zinc stearate and the like), UV stabilizers, acid scavengers,colorants or pigments, coagents (e.g., triallyl cyanurate), lubricants,antifogging agents, flow aids, processing aids, extrusion aids, couplingagents, cross-linking agents, stability control agents, nucleatingagents, surfactants, solvents, flame retardants, antistatic agents, andcombinations thereof.

The total amount of the additives can range from about greater than 0 toabout 80%, from about 0.001% to about 70%, from about 0.01% to about60%, from about 0.1% to about 50%, from about 1% to about 40%, or fromabout 10% to about 50% of the total weight of the polymer composition.Some polymer additives have been described in Zweifel Hans et al.,“Plastics Additives Handbook,” Hanser Gardner Publications, Cincinnati,Ohio, 5th edition (2001), which is incorporated herein by reference inits entirety.

Optionally, the polyfarnesene compositions disclosed herein can comprisean anti-blocking agent. In some embodiments, the polyfarnesenecompositions disclosed herein do not comprise an anti-blocking agent.The anti-blocking agent can be used to prevent the undesirable adhesionbetween touching layers of articles made from the polyfarnesenecompositions, particularly under moderate pressure and heat duringstorage, manufacture or use. Any anti-blocking agent known to a personof ordinary skill in the art may be added to the polyfarnesenecompositions disclosed herein. Non-limiting examples of anti-blockingagents include minerals (e.g., clays, chalk, and calcium carbonate),synthetic silica gel (e.g., SYLOBLOC® from Grace Davison, Columbia,Md.), natural silica (e.g., SUPER FLOSS® from Celite Corporation, SantaBarbara, Calif.), talc (e.g., OPTIBLOC® from Luzenac, Centennial,Colo.), zeolites (e.g., SIPERNAT® from Degussa, Parsippany, N.J.),aluminosilicates (e.g., SILTON® from Mizusawa Industrial Chemicals,Tokyo, Japan), limestone (e.g., CARBOREX® from Omya, Atlanta, Ga.),spherical polymeric particles (e.g., EPOSTAR®, poly(methyl methacrylate)particles from Nippon Shokubai, Tokyo, Japan and TOSPEARL®, siliconeparticles from GE Silicones, Wilton, Conn.), waxes, amides (e.g.erucamide, oleamide, stearamide, behenamide, ethylene-bis-stearamide,ethylene-bis-oleamide, stearyl erucamide and other slip agents),molecular sieves, and combinations thereof. The mineral particles canlower blocking by creating a physical gap between articles, while theorganic anti-blocking agents can migrate to the surface to limit surfaceadhesion. Where used, the amount of the anti-blocking agent in thepolymer composition can be from about greater than 0 to about 3 wt %,from about 0.0001 to about 2 wt %, from about 0.001 to about 1 wt %, orfrom about 0.001 to about 0.5 wt % of the total weight of the polymercomposition. Some anti-blocking agents have been described in ZweifelHans et al., “Plastics Additives Handbook,” Hanser Gardner Publications,Cincinnati, Ohio, 5th edition, Chapter 7, pages 585-600 (2001), which isincorporated herein by reference.

Optionally, the polyfarnesene compositions disclosed herein can comprisea plasticizer. In general, a plasticizer is a chemical that can increasethe flexibility and lower the glass transition temperature of polymers.Any plasticizer known to a person of ordinary skill in the art may beadded to the polyfarnesene compositions disclosed herein. Non-limitingexamples of plasticizers include mineral oils, abietates, adipates,alkyl sulfonates, azelates, benzoates, chlorinated paraffins, citrates,epoxides, glycol ethers and their esters, glutarates, hydrocarbon oils,isobutyrates, oleates, pentaerythritol derivatives, phosphates,phthalates, esters, polybutenes, ricinoleates, sebacates, sulfonamides,tri- and pyromellitates, biphenyl derivatives, stearates, difurandiesters, fluorine-containing plasticizers, hydroxybenzoic acid esters,isocyanate adducts, multi-ring aromatic compounds, natural productderivatives, nitriles, siloxane-based plasticizers, tar-based products,thioesters and combinations thereof. Where used, the amount of theplasticizer in the polymer composition can be from greater than 0 toabout 15 wt %, from about 0.5 to about 10 wt %, or from about 1 to about5 wt % of the total weight of the polymer composition. Some plasticizershave been described in George Wypych, “Handbook of Plasticizers,”ChemTec Publishing, Toronto-Scarborough, Ontario (2004), which isincorporated herein by reference.

In some embodiments, the polyfarnesene compositions disclosed hereinoptionally comprise an antioxidant that can prevent the oxidation ofpolymer components and organic additives in the polyfarnesenecompositions. Any antioxidant known to a person of ordinary skill in theart may be added to the polyfarnesene compositions disclosed herein.Non-limiting examples of suitable antioxidants include aromatic orhindered amines such as alkyl diphenylamines, phenyl-α-naphthylamine,alkyl or aralkyl substituted phenyl-α-naphthylamine, alkylatedp-phenylene diamines, tetramethyl-diaminodiphenylamine and the like;phenols such as 2,6-di-t-butyl-4-methylphenol;1,3,5-trimethyl-2,4,6-tris(3′,5′-di-t-butyl-4′-hydroxybenzyl)benzene;tetrakis[(methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane(e.g., IRGANOX™ 1010, from Ciba Geigy, New York); acryloyl modifiedphenols; octadecyl-3,5-di-t-butyl-4-hydroxycinnamate (e.g., IRGANOX™1076, commercially available from Ciba Geigy); phosphites andphosphonites; hydroxylamines; benzofuranone derivatives; andcombinations thereof. Where used, the amount of the antioxidant in thepolymer composition can be from about greater than 0 to about 5 wt %,from about 0.0001 to about 2.5 wt %, from about 0.001 to about 1 wt %,or from about 0.001 to about 0.5 wt % of the total weight of the polymercomposition. Some antioxidants have been described in Zweifel Hans etal., “Plastics Additives Handbook,” Hanser Gardner Publications,Cincinnati, Ohio, 5th edition, Chapter 1, pages 1-140 (2001), which isincorporated herein by reference.

In other embodiments, the polyfarnesene compositions disclosed hereinoptionally comprise an UV stabilizer that may prevent or reduce thedegradation of the polyfarnesene compositions by UV radiations. Any UVstabilizer known to a person of ordinary skill in the art may be addedto the polyfarnesene compositions disclosed herein. Non-limitingexamples of suitable UV stabilizers include benzophenones,benzotriazoles, aryl esters, oxanilides, acrylic esters, formamidines,carbon black, hindered amines, nickel quenchers, hindered amines,phenolic antioxidants, metallic salts, zinc compounds and combinationsthereof. Where used, the amount of the UV stabilizer in the polymercomposition can be from about greater than 0 to about 5 wt %, from about0.01 to about 3 wt %, from about 0.1 to about 2 wt %, or from about 0.1to about 1 wt % of the total weight of the polymer composition. Some UVstabilizers have been described in Zweifel Hans et al., “PlasticsAdditives Handbook,” Hanser Gardner Publications, Cincinnati, Ohio, 5thedition, Chapter 2, pages 141-426 (2001), which is incorporated hereinby reference.

In further embodiments, the polyfarnesene compositions disclosed hereinoptionally comprise a colorant or pigment that can change the look ofthe polyfarnesene compositions to human eyes. Any colorant or pigmentknown to a person of ordinary skill in the art may be added to thepolyfarnesene compositions disclosed herein. Non-limiting examples ofsuitable colorants or pigments include inorganic pigments such as metaloxides such as iron oxide, zinc oxide, and titanium dioxide, mixed metaloxides, carbon black, organic pigments such as anthraquinones,anthanthrones, azo and monoazo compounds, arylamides, benzimidazolones,BONA lakes, diketopyrrolo-pyrroles, dioxazines, disazo compounds,diarylide compounds, flavanthrones, indanthrones, isoindolinones,isoindolines, metal complexes, monoazo salts, naphthols, b-naphthols,naphthol AS, naphthol lakes, perylenes, perinones, phthalocyanines,pyranthrones, quinacridones, and quinophthalones, and combinationsthereof. Where used, the amount of the colorant or pigment in thepolymer composition can be from about greater than 0 to about 10 wt %,from about 0.1 to about 5 wt %, or from about 0.25 to about 2 wt % ofthe total weight of the polymer composition. Some colorants have beendescribed in Zweifel Hans et al., “Plastics Additives Handbook,” HanserGardner Publications, Cincinnati, Ohio, 5th edition, Chapter 15, pages813-882 (2001), which is incorporated herein by reference.

Optionally, the polyfarnesene compositions disclosed herein can comprisea filler which can be used to adjust, inter alia, volume, weight, costs,and/or technical performance. Any filler known to a person of ordinaryskill in the art may be added to the polyfarnesene compositionsdisclosed herein. Non-limiting examples of suitable fillers includetalc, calcium carbonate, chalk, calcium sulfate, clay, kaolin, silica,glass, fumed silica, mica, wollastonite, feldspar, aluminum silicate,calcium silicate, alumina, hydrated alumina such as alumina trihydrate,glass microsphere, ceramic microsphere, thermoplastic microsphere,barite, wood flour, glass fibers, carbon fibers, marble dust, cementdust, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide,barium sulfate, titanium dioxide, titanates and combinations thereof. Insome embodiments, the filler is barium sulfate, talc, calcium carbonate,silica, glass, glass fiber, alumina, titanium dioxide, or a mixturethereof. In other embodiments, the filler is talc, calcium carbonate,barium sulfate, glass fiber or a mixture thereof. Where used, the amountof the filler in the polymer composition can be from about greater than0 to about 80 wt %, from about 0.1 to about 60 wt %, from about 0.5 toabout 40 wt %, from about 1 to about 30 wt %, or from about 10 to about40 wt % of the total weight of the polymer composition. Some fillershave been disclosed in U.S. Pat. No. 6,103,803 and Zweifel Hans et al.,“Plastics Additives Handbook,” Hanser Gardner Publications, Cincinnati,Ohio, 5th edition, Chapter 17, pages 901-948 (2001), both of which areincorporated herein by reference.

Optionally, the polyfarnesene compositions disclosed herein can comprisea lubricant. In general, the lubricant can be used, inter alia, tomodify the rheology of the molten polyfarnesene compositions, to improvethe surface finish of molded articles, and/or to facilitate thedispersion of fillers or pigments. Any lubricant known to a person ofordinary skill in the art may be added to the polyfarnesene compositionsdisclosed herein. Non-limiting examples of suitable lubricants includefatty alcohols and their dicarboxylic acid esters, fatty acid esters ofshort-chain alcohols, fatty acids, fatty acid amides, metal soaps,oligomeric fatty acid esters, fatty acid esters of long-chain alcohols,montan waxes, polyethylene waxes, polypropylene waxes, natural andsynthetic paraffin waxes, fluoropolymers and combinations thereof. Whereused, the amount of the lubricant in the polymer composition can be fromabout greater than 0 to about 5 wt %, from about 0.1 to about 4 wt %, orfrom about 0.1 to about 3 wt % of the total weight of the polymercomposition. Some suitable lubricants have been disclosed in ZweifelHans et al., “Plastics Additives Handbook,” Hanser Gardner Publications,Cincinnati, Ohio, 5th edition, Chapter 5, pages 511-552 (2001), both ofwhich are incorporated herein by reference.

Optionally, the polyfarnesene compositions disclosed herein can comprisean antistatic agent. Generally, the antistatic agent can increase theconductivity of the polyfarnesene compositions and to prevent staticcharge accumulation. Any antistatic agent known to a person of ordinaryskill in the art may be added to the polyfarnesene compositionsdisclosed herein. Non-limiting examples of suitable antistatic agentsinclude conductive fillers (e.g., carbon black, metal particles andother conductive particles), fatty acid esters (e.g., glycerolmonostearate), ethoxylated alkylamines, diethanolamides, ethoxylatedalcohols, alkylsulfonates, alkylphosphates, quaternary ammonium salts,alkylbetaines and combinations thereof. Where used, the amount of theantistatic agent in the polymer composition can be from about greaterthan 0 to about 5 wt %, from about 0.01 to about 3 wt %, or from about0.1 to about 2 wt % of the total weight of the polymer composition. Somesuitable antistatic agents have been disclosed in Zweifel Hans et al.,“Plastics Additives Handbook,” Hanser Gardner Publications, Cincinnati,Ohio, 5th edition, Chapter 10, pages 627-646 (2001), both of which areincorporated herein by reference.

Optionally, the polyfarnesene compositions disclosed herein can comprisea blowing agent for preparing foamed articles. The blowing agents caninclude, but are not limited to, inorganic blowing agents, organicblowing agents, chemical blowing agents and combinations thereof. Someblowing agents are disclosed in Sendijarevic et al., “Polymeric FoamsAnd Foam Technology,” Hanser Gardner Publications, Cincinnati, Ohio, 2ndedition, Chapter 18, pages 505-547 (2004), which is incorporated hereinby reference.

Non-limiting examples of suitable inorganic blowing agents includecarbon dioxide, nitrogen, argon, water, air, nitrogen, and helium.Non-limiting examples of suitable organic blowing agents includealiphatic hydrocarbons having 1-6 carbon atoms, aliphatic alcoholshaving 1-3 carbon atoms, and fully and partially halogenated aliphatichydrocarbons having 1-4 carbon atoms. Non-limiting examples of suitablealiphatic hydrocarbons include methane, ethane, propane, n-butane,isobutane, n-pentane, isopentane, neopentane, and the like. Non-limitingexamples of suitable aliphatic alcohols include methanol, ethanol,n-propanol, and isopropanol. Non-limiting examples of suitable fully andpartially halogenated aliphatic hydrocarbons include fluorocarbons,chlorocarbons, and chlorofluorocarbons. Non-limiting examples ofsuitable fluorocarbons include methyl fluoride, perfluoromethane, ethylfluoride, 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane(HFC-143a), 1,1,1,2-tetrafluoro-ethane (HFC-134a), pentafluoroethane,difluoromethane, perfluoroethane, 2,2-difluoropropane,1,1,1-trifluoropropane, perfluoropropane, dichloropropane,difluoropropane, perfluorobutane, perfluorocyclobutane. Non-limitingexamples of suitable partially halogenated chlorocarbons andchlorofluorocarbons include methyl chloride, methylene chloride, ethylchloride, 1,1,1-trichloroethane, 1,1-dichloro-1-fluoroethane(HCFC-141b), 1-chloro-1,1 difluoroethane (HCFC-142b),1,1-dichloro-2,2,2-trifluoroethane (HCFC-123) and1-chloro-1,2,2,2-tetrafluoroethane(HCFC-124). Non-limiting examples ofsuitable fully halogenated chlorofluorocarbons includetrichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12),trichlorotrifluoroethane (CFC-113), 1,1,1-trifluoroethane,pentafluoroethane, dichlorotetrafluoroethane (CFC-114),chloroheptafluoropropane, and dichlorohexafluoropropane. Non-limitingexamples of suitable chemical blowing agents include azodicarbonamide,azodiisobutyro-nitrile, benezenesulfonhydrazide, 4,4-oxybenzenesulfonyl-semicarbazide, p-toluene sulfonyl semi-carbazide, bariumazodicarboxylate, N,N′-dimethyl-N,N′-dinitrosoterephthalamide, andtrihydrazino triazine. In some embodiments, the blowing agent isazodicarbonamide isobutane, CO₂, or a mixture of thereof.

The amount of the blowing agent in the polymer composition disclosedherein may be from about 0.1 to about 20 wt. %, from about 0.1 to about10 wt. %, or from about 0.1 to about 5 wt. %, based on the weight of thefarnesene interpolymer or the polymer composition. In other embodiments,the amount of the blowing agent is from about 0.2 to about 5.0 moles perkilogram of the interpolymer or polymer composition, from about 0.5 toabout 3.0 moles per kilogram of the interpolymer or polymer composition,or from about 1.0 to about 2.50 moles per kilogram of the interpolymeror polymer composition.

In some embodiments, the polyfarnesene compositions disclosed hereincomprise a slip agent. In other embodiments, the polyfarnesenecompositions disclosed herein do not comprise a slip agent. Slip is thesliding of film surfaces over each other or over some other substrates.The slip performance of films can be measured by ASTM D 1894, Static andKinetic Coefficients of Friction of Plastic Film and Sheeting, which isincorporated herein by reference. In general, the slip agent can conveyslip properties by modifying the surface properties of films; andreducing the friction between layers of the films and between the filmsand other surfaces with which they come into contact.

Any slip agent known to a person of ordinary skill in the art may beadded to the polyfarnesene compositions disclosed herein. Non-limitingexamples of the slip agents include primary amides having about 12 toabout 40 carbon atoms (e.g., erucamide, oleamide, stearamide andbehenamide); secondary amides having about 18 to about 80 carbon atoms(e.g., stearyl erucamide, behenyl erucamide, methyl erucamide and ethylerucamide); secondary-bis-amides having about 18 to about 80 carbonatoms (e.g., ethylene-bis-stearamide and ethylene-bis-oleamide); andcombinations thereof.

In some embodiments, the slip agent is a primary amide with a saturatedaliphatic group having between 18 and about 40 carbon atoms (e.g.,stearamide and behenamide). In other embodiments, the slip agent is aprimary amide with an unsaturated aliphatic group containing at leastone carbon-carbon double bond and between 18 and about 40 carbon atoms(e.g., erucamide and oleamide). In further embodiments, the slip agentis a primary amide having at least 20 carbon atoms. In furtherembodiments, the slip agent is erucamide, oleamide, stearamide,behenamide, ethylene-bis-stearamide, ethylene-bis-oleamide, stearylerucamide, behenyl erucamide or a combination thereof. In a particularembodiment, the slip agent is erucamide. In further embodiments, theslip agent is commercially available having a trade name such as ATMER™SA from Uniqema, Everberg, Belgium; ARMOSLIP® from Akzo Nobel PolymerChemicals, Chicago, Ill.; KEMAMIDE® from Witco, Greenwich, Conn.; andCRODAMIDE® from Croda, Edison, N.J. Where used, the amount of the slipagent in the polymer composition can be from about greater than 0 toabout 3 wt %, from about 0.0001 to about 2 wt %, from about 0.001 toabout 1 wt %, from about 0.001 to about 0.5 wt % or from about 0.05 toabout 0.25 wt % of the total weight of the polymer composition. Someslip agents have been described in Zweifel Hans et al., “PlasticsAdditives Handbook,” Hanser Gardner Publications, Cincinnati, Ohio, 5thedition, Chapter 8, pages 601-608 (2001), which is incorporated hereinby reference.

In some embodiments, the polyfarnesene compositions disclosed hereincomprise a tackifier. In other embodiments, the polyfarnesenecompositions disclosed herein do not comprise a tackifier. Any materialthat can be added to an elastomer to produce an adhesive can be usedherein as a tackifier. Some non-limiting examples of tackifiers includea natural and modified resin; a glycerol or pentaerythritol ester ofnatural or modified rosin; a copolymer or terpolymer of natured terpene;a polyterpene resin or a hydrogenated polyterpene resin; a phenolicmodified terpene resin or a hydrogenated derivative thereof; analiphatic or cycloaliphatic hydrocarbon resin or a hydrogenatedderivative thereof; an aromatic hydrocarbon resin or a hydrogenatedderivative thereof; an aromatic modified aliphatic or cycloaliphatichydrocarbon resin or a hydrogenated derivative thereof; or a combinationthereof. In certain embodiments, the tackifier has a ring and ball (R&B)softening point equal to or greater than 60° C., 70° C., 75° C., 80° C.,85° C., 90° C. or 100° C., as measured in accordance with ASTM 28-67,which is incorporated herein by reference. In certain embodiments, thetackifier has a R&B softening point equal to or greater than 80° C., asmeasured in accordance with ASTM 28-67.

In certain embodiments, the amount of tackifier in the polyfarnesenecompositions disclosed herein is in the range from about 0.1 wt. % toabout 70 wt. %, from about 0.1 wt. % to about 60 wt. %, from about 1 wt.% to about 50 wt. %, or from about 0.1 wt. % to about 40 wt. % or fromabout 0.1 wt. % to about 30 wt. % or from about 0.1 wt. % to about 20wt. %, or from about 0.1 wt. % to about 10 wt. %, based on the totalweight of the composition. In other embodiments, the amount of tackifierin the compositions disclosed herein is in the range from about 1 wt. %to about 70 wt. %, from about 5 wt. % to about 70 wt. %, from about 10wt. % to about 70 wt. %, from about 15 wt. % to about 70 wt. %, fromabout 20 wt. % to about 70 wt. %, or from about 25 wt. % to about 70 wt.%, based on the total weight of the composition.

Optionally, the polyfarnesene compositions disclosed herein can comprisea wax, such as a petroleum wax, a low molecular weight polyethylene orpolypropylene, a synthetic wax, a polyolefin wax, a beeswax, a vegetablewax, a soy wax, a palm wax, a candle wax or an ethylene/α-olefininterpolymer having a melting point of greater than 25° C. In certainembodiments, the wax is a low molecular weight polyethylene orpolypropylene having a number average molecular weight of about 400 toabout 6,000 g/mole. The wax can be present in the range from about 10%to about 50% or 20% to about 40% by weight of the total composition.

Optionally, the polyfarnesene compositions disclosed herein may becrosslinked, partially or completely. When crosslinking is desired, thepolyfarnesene compositions disclosed herein comprise a cross-linkingagent that can be used to effect the cross-linking of the polyfarnesenecompositions, thereby increasing their modulus and stiffness, amongother things. An advantage of a polyfarnesene composition is thatcrosslinking can occur in its side chains instead of the polymerbackbone like other polymers such as polyisoprene and polybutadiene. Anycross-linking agent known to a person of ordinary skill in the art maybe added to the polyfarnesene compositions disclosed herein.Non-limiting examples of suitable cross-linking agents include organicperoxides (e.g., alkyl peroxides, aryl peroxides, peroxyesters,peroxycarbonates, diacylperoxides, peroxyketals, and cyclic peroxides)and silanes (e.g., vinyltrimethoxysilane, vinyltriethoxysilane,vinyltris(2-methoxyethoxy)silane, vinyltriacetoxysilane,vinylmethyldimethoxysilane, and3-methacryloyloxypropyltrimethoxysilane). Where used, the amount of thecross-linking agent in the polymer composition can be from about greaterthan 0 to about 20 wt. %, from about 0.1 wt. % to about 15 wt. %, orfrom about 1 wt. % to about 10 wt. % of the total weight of the polymercomposition. Some suitable cross-linking agents have been disclosed inZweifel Hans et al., “Plastics Additives Handbook,” Hanser GardnerPublications, Cincinnati, Ohio, 5th edition, Chapter 14, pages 725-812(2001), both of which are incorporated herein by reference.

In some embodiments, the farnesene interpolymers disclosed hereinincludes farnesene-modified polymers prepared by copolymerizing one ormore farnesene with one or more vinyl monomers. In certain embodiments,the unmodified polymer derived from the one or more vinyl monomers canbe any known olefin homopolymer or interpolymer. In further embodiments,none of the one or more other vinyl monomers has an unsaturated sidechain capable of reacting with a cross-linking agent. Because of theunsaturated side chains derived from the farnesene, thefarnesene-modified polymer disclosed herein can be cross-linked by across-linking agent disclosed herein.

In certain embodiments, the amount of the farnesene in thefarnesene-modified polymer disclosed herein is from about 1 wt. % toabout 20 wt. %, from about 1 wt. % to about 10 wt. %, from about 1 wt. %to about 7.5 wt. %, from about 1 wt. % to about 5 wt. %, from about 1wt. % to about 4 wt. %, from about 1 wt. % to about 3 wt. %, or fromabout 1 wt. % to about 2 wt. %, based on the total weight of thefarnesene-modified polymer. In other embodiments, the amount of the oneor more other vinyl monomers in the farnesene-modified polymer disclosedherein is from about 80 wt. % to about 99 wt. %, from about 90 wt. % toabout 99 wt. %, from about 92.5 wt. % to about 99 wt. %, from about 95wt. % to about 99 wt. %, from about 96 wt. % to about 99 wt. %, fromabout 97 wt. % to about 99 wt. %, or from about 98 wt. % to about 99 wt.%, based on the total weight of the farnesene-modified polymer.

The cross-linking of the polyfarnesene compositions can also beinitiated by any radiation means known in the art, including, but notlimited to, electron-beam irradiation, beta irradiation, gammairradiation, corona irradiation, and UV radiation with or withoutcross-linking catalyst. U.S. patent application Ser. No. 10/086,057(published as US2002/0132923 A1) and U.S. Pat. No. 6,803,014 discloseelectron-beam irradiation methods that can be used in embodiments of theinvention.

Irradiation may be accomplished by the use of high energy, ionizingelectrons, ultra violet rays, X-rays, gamma rays, beta particles and thelike and combination thereof. Preferably, electrons are employed up to70 megarads dosages. The irradiation source can be any electron beamgenerator operating in a range of about 150 kilovolts to about 6megavolts with a power output capable of supplying the desired dosage.The voltage can be adjusted to appropriate levels which may be, forexample, 100,000, 300,000, 1,000,000 or 2,000,000 or 3,000,000 or6,000,000 or higher or lower. Many other apparati for irradiatingpolymeric materials are known in the art. The irradiation is usuallycarried out at a dosage between about 3 megarads to about 35 megarads,preferably between about 8 to about 20 megarads. Further, theirradiation can be carried out conveniently at room temperature,although higher and lower temperatures, for example, 0° C. to about 60°C., may also be employed. Preferably, the irradiation is carried outafter shaping or fabrication of the article. Also, in a preferredembodiment, the farnesene interpolymer which has been incorporated witha pro-rad additive is irradiated with electron beam radiation at about 8to about 20 megarads.

Crosslinking can be promoted with a crosslinking catalyst, and anycatalyst that will provide this function can be used. Suitable catalystsgenerally include organic bases; carboxylic acids; and organometalliccompounds including organic titanates and complexes or carboxylates oflead, cobalt, iron, nickel, zinc and tin; dibutyltindilaurate,dioctyltinmaleate, dibutyltindiacetate, dibutyltindioctoate, stannousacetate, stannous octoate, lead naphthenate, zinc caprylate, cobaltnaphthenate; and the like. The catalyst (or mixture of catalysts) ispresent in a catalytic amount, typically between about 0.015 and about0.035 phr.

Representative pro-rad additives include, but are not limited to, azocompounds, organic peroxides and polyfunctional vinyl or allyl compoundssuch as, for example, triallyl cyanurate, triallyl isocyanurate,pentaerthritol tetramethacrylate, glutaraldehyde, ethylene glycoldimethacrylate, diallyl maleate, dipropargyl maleate, dipropargylmonoallyl cyanurate, dicumyl peroxide, di-tert-butyl peroxide, t-butylperbenzoate, benzoyl peroxide, cumene hydroperoxide, t-butyl peroctoate,methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di(t-butyl peroxy)hexane,lauryl peroxide, tert-butyl peracetate, azobisisobutyl nitrite and thelike and combination thereof. Preferred pro-rad additives for use in thepresent invention are compounds which have poly-functional (i.e. atleast two) moieties such as C═C, C═N or C═O.

At least one pro-rad additive can be introduced to the farneseneinterpolymer by any method known in the art. However, preferably thepro-rad additive(s) is introduced via a masterbatch concentratecomprising the same or different base resin as the farneseneinterpolymer. Preferably, the pro-rad additive concentration for themasterbatch is relatively high e.g., about 25 weight percent (based onthe total weight of the concentrate).

The at least one pro-rad additive is introduced to the polyfarnesene inany effective amount. Preferably, the at least one pro-rad additiveintroduction amount is from about 0.001 to about 5 weight percent, morepreferably from about 0.005 to about 2.5 weight percent and mostpreferably from about 0.015 to about 1 weight percent (based on thetotal weight of the farnesene interpolymer.

In addition to electron-beam irradiation, crosslinking can also beeffected by UV irradiation. The method comprises mixing aphotoinitiator, with or without a photocrosslinker, with a polymerbefore, during, or after a fiber is formed and then exposing the fiberwith the photoinitiator to sufficient UV radiation to crosslink thepolymer to the desired level. The photoinitiators used in the practiceof the invention are aromatic ketones, e.g., benzophenones ormonoacetals of 1,2-diketones. The primary photoreaction of themonoacetals is the homolytic cleavage of the α-bond to give acyl anddialkoxyalkyl radicals. This type of α-cleavage is known as a NorrishType I reaction which is more fully described in W. Horspool and D.Armesto, “Organic Photochemistry: A Comprehensive Treatment,” EllisHorwood Limited, Chichester, England, 1992; J. Kopecky, “OrganicPhotochemistry: A Visual Approach,” VCH Publishers, Inc., New York, N.Y.1992; N. J. Turro, et al., Acc. Chem. Res., 1972, 5, 92; and J. T.Banks, et al., J. Am. Chem. Soc., 1993, 115, 2473. The synthesis ofmonoacetals of aromatic 1,2 diketones, Ar—CO—C(OR)₂—Ar′ is described inU.S. Pat. No. 4,190,602 and Ger. Offen. 2,337,813. The preferredcompound from this class is 2,2-dimethoxy-2-phenylacetophenone,C₆H₅—CO—C(OCH₃)₂—C₆H₅, which is commercially available from Ciba-Geigyas IRGACURE™ 651. Examples of other aromatic ketones useful herein asphotoinitiators are IRGACURE™ 184, 369, 819, 907 and 2959, all availablefrom Ciba-Geigy.

In one embodiment of the invention, the photoinitiator is used incombination with a photocrosslinker. Any photocrosslinker that will uponthe generation of free radicals, link two or more polyolefin backbonestogether through the formation of covalent bonds with the backbones canbe used herein. Preferably these photocrosslinkers are polyfunctional,i.e., they comprise two or more sites that upon activation will form acovalent bond with a site on the backbone of the polyfarnesene.Representative photocrosslinkers include, but are not limited topolyfunctional vinyl or allyl compounds such as, for example, triallylcyanurate, triallyl isocyanurate, pentaerthritol tetramethacrylate,ethylene glycol dimethacrylate, diallyl maleate, dipropargyl maleate,dipropargyl monoallyl cyanurate and the like. Preferredphotocrosslinkers for use in the present invention are compounds whichhave polyfunctional (i.e., at least two) moieties. Particularlypreferred photocrosslinkers are triallylcyanurate (TAC) andtriallylisocyanurate (TAIC).

Certain compounds act as both a photoinitiator and a photocrosslinkerherein. These compounds are characterized by the ability to generate twoor more reactive species (e.g., free radicals, carbenes, nitrenes, etc.)upon exposure to UV-light and to subsequently covalently bond with twopolymer chains. Any compound that can perform these two functions can beused herein, and representative compounds include sulfonyl azides.

In another embodiment, the polyfarnesene is subjected to secondarycrosslinking, i.e., crosslinking other than and in addition tophotocrosslinking In this embodiment, the photoinitiator is used eitherin combination with a nonphotocrosslinker, e.g., a silane, or thepolyfarnesene is subjected to a secondary crosslinking procedure, e.g,exposure to E-beam radiation. The use of a photocrosslinker in thisembodiment is optional.

At least one photoadditive, i.e., photoinitiator and optionalphotocrosslinker, can be introduced to the polyfarnesene by any methodknown in the art. However, preferably the photoadditive(s) is (are)introduced via a masterbatch concentrate comprising the polyfarnesene.Preferably, the photoadditive concentration for the masterbatch is highthan about 10 wt. %, about 15 wt. %, about 20 wt. %, or about 25 wt. %,based on the total weight of the concentrate.

The at least one photoadditive is introduced to the polyfarnesene in anyeffective amount. Preferably, the at least one photoadditiveintroduction amount is from about 0.001 wt. % to about 5 wt. %, morepreferably from about 0.005 wt. % to about 2.5 wt. % and most preferablyfrom about 0.015 wt. % to about 1 wt. %, based on the total weight ofthe polyfarnesene.

The photoinitiator(s) and optional photocrosslinker(s) can be addedduring different stages of the fiber or film manufacturing process. Ifphotoadditives can withstand the extrusion temperature, a polyolefinresin can be mixed with additives before being fed into the extruder,e.g., via a masterbatch addition. Alternatively, additives can beintroduced into the extruder just prior the slot die, but in this casethe efficient mixing of components before extrusion is important. Inanother approach, polyolefin fibers can be drawn without photoadditives,and a photoinitiator and/or photocrosslinker can be applied to theextruded fiber via a kiss-roll, spray, dipping into a solution withadditives, or by using other industrial methods for post-treatment. Theresulting fiber with photoadditive(s) is then cured via electromagneticradiation in a continuous or batch process. The photo additives can beblended with the polyolefin using conventional compounding equipment,including single and twin-screw extruders.

The power of the electromagnetic radiation and the irradiation time arechosen so as to allow efficient crosslinking without polymer degradationand/or dimensional defects. The preferred process is described in EP 0490 854 B1. Photoadditive(s) with sufficient thermal stability is (are)premixed with a polyolefin resin, extruded into a fiber, and irradiatedin a continuous process using one energy source or several units linkedin a series. There are several advantages to using a continuous processcompared with a batch process to cure a fiber or sheet of a knittedfabric which are collected onto a spool.

Irradiation may be accomplished by the use of UV-radiation. Preferably,UV-radiation is employed up to the intensity of 100 J/cm². Theirradiation source can be any UV-light generator operating in a range ofabout 50 watts to about 25000 watts with a power output capable ofsupplying the desired dosage. The wattage can be adjusted to appropriatelevels which may be, for example, 1000 watts or 4800 watts or 6000 wattsor higher or lower. Many other apparati for UV-irradiating polymericmaterials are known in the art. The irradiation is usually carried outat a dosage between about 3 J/cm² to about 500 J/scm²′, preferablybetween about 5 J/cm² to about 100 J/cm². Further, the irradiation canbe carried out conveniently at room temperature, although higher andlower temperatures, for example 0° C. to about 60° C., may also beemployed. The photocrosslinking process is faster at highertemperatures. Preferably, the irradiation is carried out after shapingor fabrication of the article. In a preferred embodiment, thepolyfarnesene which has been incorporated with a photoadditive isirradiated with UV-radiation at about 10 J/cm² to about 50 J/cm².

Blending of the Ingredients of the Polymer Compositions

The ingredients of the polyfarnesene compositions, i.e., the farneseneinterpolymer, the additive, the optional second polymer (e.g.,polyethylene, and polypropylene) and additives (e.g., the cross-linkingagent) can be mixed or blended using methods known to a person ofordinary skill in the art. Non-limiting examples of suitable blendingmethods include melt blending, solvent blending, extruding, and thelike.

In some embodiments, the ingredients of the polyfarnesene compositionsare melt blended by a method as described by Guerin et al. in U.S. Pat.No. 4,152,189. First, all solvents, if there are any, are removed fromthe ingredients by heating to an appropriate elevated temperature ofabout 100° C. to about 200° C. or about 150° C. to about 175° C. at apressure of about 5 torr (667 Pa) to about 10 ton (1333 Pa). Next, theingredients are weighed into a vessel in the desired proportions and thefoam is formed by heating the contents of the vessel to a molten statewhile stirring.

In other embodiments, the ingredients of the articles are processedusing solvent blending. First, the ingredients of the desired foam aredissolved in a suitable solvent and the mixture is then mixed orblended. Next, the solvent is removed to provide the foam.

In further embodiments, physical blending devices that can providedispersive mixing, distributive mixing, or a combination of dispersiveand distributive mixing can be used in preparing homogenous blends. Bothbatch and continuous methods of physical blending can be used.Non-limiting examples of batch methods include those methods usingBRABENDER® mixing equipments (e.g., BRABENDER PREP CENTER®, availablefrom C. W. Brabender Instruments, Inc., South Hackensack, N.J.) orBANBURY® internal mixing and roll milling (available from FarrelCompany, Ansonia, Conn.) equipment. Non-limiting examples of continuousmethods include single screw extruding, twin screw extruding, diskextruding, reciprocating single screw extruding, and pin barrel singlescrew extruding. In some embodiments, the additives can be added into anextruder through a feed hopper or feed throat during the extrusion ofthe farnesene interpolymer, the optional second polymer or the foam. Themixing or blending of polymers by extrusion has been described in C.Rauwendaal, “Polymer Extrusion”, Hanser Publishers, New York, N.Y.,pages 322-334 (1986), which is incorporated herein by reference.

When one or more additives are required in the polyfarnesenecompositions, the desired amounts of the additives can be added in onecharge or multiple charges to the farnesene interpolymer, the secondpolymer or the polymer composition. Furthermore, the addition can takeplace in any order. In some embodiments, the additives are first addedand mixed or blended with the farnesene interpolymer and then theadditive-containing interpolymer is blended with the second polymer. Inother embodiments, the additives are first added and mixed or blendedwith the second polymer and then the additive-containing second polymeris blended with the farnesene interpolymer. In further embodiments, thefarnesene interpolymer is blended with the second polymer first and thenthe additives are blended with the polymer composition.

The ingredients of the polymer composition can be mixed or blended inany suitable mixing or blending devices known to skilled artisans. Theingredients in the polymer composition can then be mixed at atemperature below the decomposition temperature of the blowing agent andthe cross-linking agent to ensure that all ingredients are homogeneouslymixed and remain intact. After the polymer composition is relativelyhomogeneously mixed, the composition is shaped and then exposed toconditions (e.g. heat, pressure, shear, etc.) over a sufficient periodof time to activate the blowing agent and the cross-linking agent tomake the foam.

Applications of the Compositions Comprising the Polyfarnesenes

The polyfarnesenes or polyfarnesene compositions disclosed herein can beused for a wide variety of applications. For example, they can be usedin a variety of conventional thermoplastic fabrication processes toproduce useful articles, including objects comprising at least one filmlayer, such as a monolayer film, or at least one layer in a multilayerfilm prepared by cast, blown, calendered, or extrusion coatingprocesses; molded articles, such as blow molded, injection molded, orrotomolded articles; extrusions; fibers; and woven or non-woven fabrics.Thermoplastic compositions comprising the present polymers, includeblends with other natural or synthetic polymers, additives, reinforcingagents, ignition resistant additives, antioxidants, stabilizers,colorants, extenders, crosslinkers, blowing agents, and plasticizers. Ofparticular utility are multi-component fibers such as core/sheathfibers, having an outer surface layer, comprising at least in part, oneor more polymers of the invention.

Fibers that may be prepared from the polyfarnesenes or polyfarnesenecompositions disclosed herein include staple fibers, tow,multicomponent, sheath/core, twisted, and monofilament. Any fiberforming processes can be used herein. For example, suitable fiberforming processes include spinbonded, melt blown techniques, gel spunfibers, woven and nonwoven fabrics, or structures made from such fibers,including blends with other fibers, such as polyester, nylon or cotton,thermoformed articles, extruded shapes, including profile extrusions andco-extrusions, calendared articles, and drawn, twisted, or crimped yarnsor fibers. The polyfarnesenes or polyfarnesene compositions disclosedherein are also useful for wire and cable coating operations, as well asin sheet extrusion for vacuum forming operations, and forming moldedarticles, including the use of injection molding, blow molding process,or rotomolding processes. The polyfarnesenes or polyfarnesenecompositions disclosed herein can also be formed into fabricatedarticles such as those previously mentioned using conventionalpolyolefin processing techniques which are well known to those skilledin the art of polyolefin processing.

Dispersions (both aqueous and non-aqueous) can also be formed using thepolyfarnesenes or polyfarnesene compositions disclosed herein. Frothedfoams comprising the polyfarnesenes or polyfarnesene compositionsdisclosed herein can also be formed. The polymers may also becrosslinked by any known means, such as the use of peroxide, electronbeam, silane, azide, or other cross-linking technique. The polymers canalso be chemically modified, such as by grafting (for example by use ofmaleic anhydride (MAH), silanes, or other grafting agent), halogenation,amination, sulfonation, or other chemical modification.

Suitable end uses for the foregoing products include elastic films andfibers; soft touch goods, such as tooth brush handles and appliancehandles; gaskets and profiles; adhesives (including hot melt adhesivesand pressure sensitive adhesives); footwear (including shoe soles andshoe liners); auto interior parts and profiles; foam goods (both openand closed cell); impact modifiers for other thermoplastic polymers suchas high density polyethylene, isotactic polypropylene, or other olefinpolymers; coated fabrics; hoses; tubing; weather stripping; cap liners;flooring; and viscosity index modifiers, also known as pour pointmodifiers, for lubricants.

The polyfarnesene compositions disclosed herein can also be used tomanufacture articles for various applications such as the automotive,construction, medical, food and beverage, electrical, appliance,business machine, and consumer markets. In some embodiments, thepolyfarnesene compositions are used to manufacture molded parts orarticles selected from toys, grips, soft touch handles, bumper rubstrips, floorings, auto floor mats, wheels, casters, furniture andappliance feet, tags, seals, gaskets such as static and dynamic gaskets,automotive doors, bumper fascia, grill components, rocker panels, hoses,linings, office supplies, seals, liners, diaphragms, tubes, lids,stoppers, plunger tips, delivery systems, kitchen wares, shoes, shoebladders and shoe soles.

In some embodiments, the polyfarnesene compositions disclosed herein areused to prepare molded articles, films, sheets and foams with knownpolymer processes such as extrusion (e.g., sheet extrusion and profileextrusion); molding (e.g., injection molding, rotational molding, andblow molding); fiber spinning; and blown film and cast film processes.In general, extrusion is a process by which a polymer is propelledcontinuously along a screw through regions of high temperature andpressure where it is melted and compacted, and finally forced through adie. The extruder can be a single screw extruder, a multiple screwextruder, a disk extruder or a ram extruder. The die can be a film die,blown film die, sheet die, pipe die, tubing die or profile extrusiondie. The extrusion of polymers has been described in C. Rauwendaal,“Polymer Extrusion”, Hanser Publishers, New York, N.Y. (1986); and M. J.Stevens, “Extruder Principals and Operation,” Ellsevier Applied SciencePublishers, New York, N.Y. (1985), both of which are incorporated hereinby reference in their entirety.

Injection molding is also widely used for manufacturing a variety ofplastic parts for various applications. In general, injection molding isa process by which a polymer is melted and injected at high pressureinto a mold, which is the inverse of the desired shape, to form parts ofthe desired shape and size. The mold can be made from metal, such assteel and aluminum. The injection molding of polymers has been describedin Beaumont et al., “Successful Injection Molding: Process, Design, andSimulation,” Hanser Gardner Publications, Cincinnati, Ohio (2002), whichis incorporated herein by reference in its entirety.

Molding is generally a process by which a polymer is melted and led intoa mold, which is the inverse of the desired shape, to form parts of thedesired shape and size. Molding can be pressureless orpressure-assisted. The molding of polymers is described in Hans-GeorgElias “An Introduction to Plastics,” Wiley-VCH, Weinhei, Germany, pp.161-165 (2003), which is incorporated herein by reference.

Rotational molding is a process generally used for producing hollowplastic products. By using additional post-molding operations, complexcomponents can be produced as effectively as other molding and extrusiontechniques. Rotational molding differs from other processing methods inthat the heating, melting, shaping, and cooling stages all occur afterthe polymer is placed in the mold, therefore no external pressure isapplied during forming. The rotational molding of polymers has beendescribed in Glenn Beall, “Rotational Molding: Design, Materials &Processing,” Hanser Gardner Publications, Cincinnati, Ohio (1998), whichis incorporated herein by reference in its entirety.

Blow molding can be used for making hollow plastics containers. Theprocess includes placing a softened polymer in the center of a mold,inflating the polymer against the mold walls with a blow pin, andsolidifying the product by cooling. There are three general types ofblow molding: extrusion blow molding, injection blow molding, andstretch blow molding. Injection blow molding can be used to processpolymers that cannot be extruded. Stretch blow molding can be used fordifficult to blow crystalline and crystallizable polymers such aspolypropylene. The blow molding of polymers has been described in NormanC. Lee, “Understanding Blow Molding,” Hanser Gardner Publications,Cincinnati, Ohio (2000), which is incorporated herein by reference inits entirety.

The following examples are presented to exemplify embodiments of theinvention but are not intended to limit the invention to the specificembodiments set forth. Unless indicated to the contrary, all parts andpercentages are by weight. All numerical values are approximate. Whennumerical ranges are given, it should be understood that embodimentsoutside the stated ranges may still fall within the scope of theinvention. Specific details described in each example should not beconstrued as necessary features of the invention.

EXAMPLES

Purification of Starting Materials

β-farnesene having 97.6% purity by weight was obtained from AmyrisBiotechnologies Inc., Emeryville, Calif. β-Farnesene includedhydrocarbon-based impurities such as zingiberene, bisabolene, farneseneepoxide, farnesol isomer, E,E-farnesol, squalene, ergosterol, and somedimers of farnesene. β-farnesene was purified with a 3 Å molecular sieveto remove the impurities and were then redistilled under nitrogenatmosphere to improve purity. Cyclohexane was distilled under nitrogenatmosphere to eliminate moisture and stored with a drying agent.

Differential Scanning calorimetry

A TA Q200 differential scanning calorimeter was utilized to determineglass transition temperatures (T_(g)) of polymer samples disclosedherein. A 5 mg sample was placed in an aluminum pan. An empty referencepan and the sample pan were maintained within ±0.01 mg. Samples werescanned from about −175° C. to about 75° C. at a rate of 10° C./min.T_(g) was identified as a step change transition in the heat flow. Themid-point of the transition was reported as the T_(g) of the sample.

Gel Permeation Chromatography

GPC was utilized to determine the molecular weights and polydispersitiesof polymer samples. A Waters 2414 refractive index detector was usedwith a Waters 1515 isocratic HPLC pump. HPLC grade tetrahydrofuran wasused as solvent. Polydispersed fractions were collected from GPC. Themolecular weight of a sample was generally recorded as the numberaveraged molecular weight (M_(n)) or the weight average (M_(w)). Whenthere were overlapping peaks which prohibited the determination of aunique polydispersity of each peak, a peak molecular weight (M_(p)) wasincorporated herein.

Thermal Gravimetric Analysis

The degradation temperatures of samples were determined by thermalgravimetric analysis (TGA). About 20 mg of a sample was placed in atared pan. The pan was then loaded into a furnace. Air flow was allowedto equilibrate. The sample was then heated from room temperature to 580°C. at 10° C./min. Temperatures for 1% and 5% weight loss of samples werereported respectively.

Ultraviolet-Visible Spectroscopy

Ultraviolet-visible (UV-Vis) spectroscopy was utilized to monitormonomer consumption during the reaction. The reaction was allowed tocontinue until all monomers had been consumed. A Shimadzu UV-2450 UV-Visspectrophotometer was utilized. Background measurement was averaged fromfive measurements with an empty quartz cuvette. Aliquots wereperiodically taken from the reaction vessel, which was then placed in asquare quartz cuvette with having 1 cm beam distance. The absorbance ofthe sample is directly proportional to the concentration of the monomerin the aliquot. The progress of the reaction was monitored by UV-Visspectroscopy with the characteristic absorption peak of β-farnesene at230 nm.

Tensile Strength

Tensile strength of samples were determined using an INSTRON™ tensiletester. A sample was cast into films and cut to the appropriatedimensions. The thickness and width of the sample after processing weremeasured. A gauge length of 2.54 cm was used with a crosshead speed 25mm/min.

Lap Test

Lap test was used to characterize adhesive properties of samples. Twosubstrates were held together by an adhesive. Substrates were thenpulled apart, shearing the adhesive. The construct fails in one of threeways. When the substrate failed, it was called a substrate failure. Whenthe adhesive was torn apart, it was called a cohesive failure. When theinterface between the substrate and adhesive failed, it was called anadhesive failure. An INSTRON™ tensile tester was used to characterizethe forces involved in the failure. The adhesive was applied to a 2 cm²section of the substrate with a crosshead speed of 25 mm/min. Aluminumwas used as the substrate. Aluminum was cleaned with acetone beforebonding.

¹H and ¹³C Nuclear Magnetic Resonance

¹H and ¹³C Nuclear Magnetic Resonance was utilized to characterizechemical microstructures of the samples. A Varian Mercury 300 MHz NMRwas utilized for these measurements. Deuterated chloroform was used asthe solvent. Several measurements were repeated for collecting spectra.

Example 1 1,4-polyfarnesene Having a M_(n) 105,000

To a dried three-neck reactor under argon atmosphere, a pre-driedsolution comprising 92.29 g of β-farnesene in 13.7% in cyclohexane wasadded. n-Butyl lithium (1.85×10⁻³ mol, obtained from Acros, MorrisPlains, N.J.) was added into the reactor as an initiator, and thereactor was heated at about 50° C. for about 19 hours, until allβ-farnesene was consumed, monitored by UV-Vis spectroscopy. Example 1was precipitated from the reaction mixture with a 1% solution of ethanoland t-butyl catechol (obtained from Sigma-Aldrich, St. Louis, Mo.).After drying in a vacuum oven at about 60° C. for about 2 hours, Example1 was kept under vacuum for about 16 hours. Afterwards, Example 1,collected at 89.83 g (yield 97%), was stored in a refrigerator toprevent any crosslinking before characterization.

The progress of synthesizing Example 1 was monitored by thedisappearance of β-farnesene, as measured by UV-Vis in the reactionmixture. FIG. 1 shows the Ultraviolet-Visible (UV-Vis) spectra ofExample 1 and β-farnesene. The characteristic absorption peak ofβ-farnesene at 230 nm is present in the UV-Vis spectrum for β-farnesenein FIG. 1, but absent in the UV-Vis spectrum for Example 1 in FIG. 1.

The molecular weight and polydispersity of Example 1 were determined byGPC. FIG. 2 shows the GPC curve of Example 1. The number averagemolecular weight (M_(n)), weight average molecular weight (M_(w)), peakmolecular weight (M_(p)), z average molecular weight (M_(z)), z+1average molecular weight (M_(z+1)), M_(w)/M_(n) (i.e., polydispersity),M_(z)/M_(w), and M_(z+1)/M_(w) of Example 1 are shown in Table 1. Thedefinitions of M_(n), M_(w), M_(z), M_(z+1), M_(p), and polydispersitycan be found in Technical Bulletin TB021, “Molecular Weight Distributionand Definitions of MW Averages,” published by Polymer Laboratories,which is incorporated herein by reference. Some methods of measuring themolecular weights of polymers can be found in the book by Malcolm P.Stevens, “Polymer Chemistry: An Introduction,” Oxford University Press,Chapter 2 (1999), pp. 35-58, which is incorporated herein by reference.The number of farnesene units in Example 1 was calculated to be about490.

TABLE 1 Properties Example 1 M_(n) 104,838 g/mol M_(w) 147,463 g/molM_(p) 144,216 g/mol M_(z) 207,084 g/mol M_(z+1) 314,887 g/molPolydispersity 1.406588 M_(z)/M_(w) 1.404311 M_(z+1)/M_(w) 2.135360

FIG. 3 shows the ¹³C NMR spectrum of Example 1. Peaks at 77.28 ppm,77.02 ppm, and 76.77 ppm were peaks associated with the deuteratedchloroform used for collecting the ¹³C NMR spectrum. The characteristicpeak identifying Example 1 was at 139.05 ppm.

FIG. 4 shows the ¹H NMR spectrum of Example 1. Peaks at 4.85 ppm and4.81 ppm were peaks associated with 3,4-microstructure. Peaks at 5.17ppm, 5.16 ppm, 5.14 ppm, and 5.13 ppm were peaks associated with 1,4-and 3,4-microstructures. Based on the areas under the peaks of FIG. 4,about 12% of farnesene units in Example 1 was found to have3,4-microstructure.

The DSC curve of Example 1 is shown in FIG. 5. The thermalcharacteristics of Example 1 were measured by DSC. The T_(g) of Example1 was found to be about −76° C. No other thermal event was detectedbetween −175° C. and 75° C.

The TGA curve of Example 1 measured in air is shown in FIG. 6. Thedecomposition temperature of Example 1 in air was determined by TGA. The1% weight loss of Example 1 in air was recorded at 210° C. and the 5%weight loss of Example 1 in air was recorded at 307° C.

The TGA curve of Example 1 measured under nitrogen atmosphere is shownin FIG. 7. The 1% weight loss of Example 1 under nitrogen atmosphere wasrecorded at 307° C. and the 5% weight loss of Example 1 under nitrogenatmosphere was recorded at 339° C.

Example 1 was observed to be tacky. The lap test results of Example 1are shown in FIG. 8. The adhesive capability of Example 1 was measuredby the lap test. The adhesive energy of Example 1 was found to be about11,400 J/m² with a peak stress of about 314 N/m².

Example 2 1,4-polyfarnesene Having a M_(n) of 245,000

Example 2 is a 1,4-polyfarnesene having a M_(n) of about 245,000 g/mol.Example 2 was synthesized similarly according to the procedure forExample 1, except sec-butyl lithium was used as the initiator. The netweight of Example 2 was found to be 83.59 g (yield 71.4%). The yield islower because aliquots were removed to monitor the progression of thereaction.

The molecular weight and polydispersity of Example 2 were determined byGPC. FIG. 9 shows the GPC curve of Example 2. The M_(n), M_(w), M_(p),M_(z), M_(z+1), polydispersity, M_(z)/M_(w), and M_(z+1)/M_(w) ofExample 2 are shown in Table 2. The number of farnesene units in Example2 was calculated to be about 2000. Because of the increased molecularweight of Example 2, it had a higher level of entanglement and longerrelaxation time than Example 1.

TABLE 2 Properties Example 2 M_(n) 244,747 g/mol M_(w) 457,340 g/molM_(p) 501,220 g/mol M_(z) 768,187 g/mol M_(z+1) 1,132,362 g/mol  Polydispersity 1.868622 M_(z)/M_(w) 1.679684 M_(z+1)/M_(w) 2.475971

The DSC curve of Example 2 is shown in FIG. 10. The thermalcharacteristics of Example 2 were measured by DSC. The T_(g) of Example2 was found to be about −76° C.

The tensile test results of Example 2 are shown in FIG. 11. The tensilestrength of Example 2 was measured by a tensile test. Example 2 wasobserved to be soft, tacky and yielded quickly. As shown in FIG. 11, thepeak elongation of Example 2 was found to be about 6% with a maximumtensile strength of about 19 psi. The modulus of Example 2 wascalculated to be about 4.6 kpsi. Example 2 continued to yield to about40% elongation.

Example 3 3,4-polyfarnesene

Example 3 was synthesized similarly according to the procedure forExample 1 except that n-butyl lithium (1.71×10⁻³ mol) was added in thepresence of N,N,N′,N′-tetramethylethylenediamine (1.71×10⁻³ mol, TMEDA,obtained from Sigma-Aldrich, St. Louis, Mo.). The net weight of Example3 was found to be 82.72 g (yield 97%).

The molecular weight and polydispersity of Example 3 were determined byGPC. FIG. 12 shows the GPC curve of Example 3. The two peaks in FIG. 12indicated that two distinct weight fractions formed in Example 3. TheM_(n), M_(w), M_(z), M_(Z+1), polydispersity, M_(z)/M_(w), andM_(z+1)/M_(w) of Example 3 are shown in Table 3. The M_(p) of the firstpeak in FIG. 12 was about 97,165 g/mol. The M_(p) of the second peak inFIG. 12 was about 46,582 g/mol. The number of farnesene units in Example3 was calculated to be about 240.

TABLE 3 Properties Example 3 M_(n) 45,818 g/mol M_(w) 47,644 g/mol M_(z)49,134 g/mol M_(z+1) 50,527 g/mol Polydispersity 1.039844 M_(z)/M_(w)1.031269 M_(z+1)/M_(w) 1.060509

FIG. 13 shows the ¹³C NMR spectrum of Example 3. Peaks at 77.33 ppm,77.07 ppm, and 76.82 ppm were peaks of deuterated chloroform used forcollecting the ¹³C NMR spectrum. The characteristic peak identifyingExample 1 at 139.05 ppm was absent in FIG. 13, indicating a regularmicrostructure of Example 3.

FIG. 14 shows the ¹H NMR spectrum of Example 3. Peaks at 4.85 ppm and4.81 ppm were peaks associated with 3,4-microstructure. Peaks at 5.21ppm, 5.19 ppm, 5.18 ppm, 5.16 ppm and 5.15 ppm were peaks associatedwith 1,4- and 3,4-microstructures. Based on the areas under the peaks ofFIG. 14, about 10% of farnesene units in Example 3 was found to have1,4-microstructure.

The DSC curve of Example 3 is shown in FIG. 15. The thermalcharacteristics of Example 3 were measured by DSC. The T_(g) of Example3 was found to be about −76° C. No other thermal event was detectedbetween −175° C. and 75° C.

The TGA curve of Example 1 measured in air is shown in FIG. 16. Thedecomposition temperature of Example 1 in air was determined by TGA. The1% weight loss of Example 1 in air was recorded at 191° C. and the 5%weight loss of Example 1 in air was recorded at 265° C.

Example 3 was observed to be a highly tacky viscous fluid. The lap testresults of Example 3 are shown in FIG. 17. The adhesive capability ofExample 3 was measured by the lap test. The adhesive energy of Example 3was found to be about 12,900 J/m² with a peak stress of about 430 N/m².

Example 4 Polystyrene-1,4-polyfarnesene-polystyrene

To a first dried three neck reactor under argon atmosphere, a pre-driedsolution of 12% β-farnesene in cyclohexane was added. To a second driedthree neck reactor under argon atmosphere, a 20.65 g solution of 10%styrene in cyclohexane was added. Afterwards, to the styrene solution,n-butyl lithium (6.88×10⁻⁴ mol) was added into the reactor as aninitiator, and the reactor was heated at about 50° C. for about 16hours, until all styrene was consumed, as monitored by GPC. Then, 161.8β-farnesene solution (i.e., 19.61 g of β-farnesene) was transferred tothe reactor under argon atmosphere. The reaction was allowed to reactuntil completion for about 7 hours, monitored by GPC. Three equalaliquots of dichlorosilane coupling agent (3.44×10⁻⁴ mol, obtained fromAcros, Morris Plains, N.J.) were then added into the reactor such thatthe mole ratio of Li to Cl of the reaction mixture was 1:2. The reactionmixture was allowed to react until completion as indicated by a colorchange from yellow to clear in the reactor. Example 4 was precipitatedfrom the reaction mixture with a 1% solution of t-butyl catachol inethanol. After drying in a vacuum oven at about 60° C. for about 2hours, Example 4 was kept under vacuum for about 16 hours. Afterwards,Example 4, collected at 39.15 g (yield 97%), was stored in arefrigerator to prevent any crosslinking before characterization.

The GPC curve of polystyrene is shown in FIG. 18. The progress ofpolystyrene synthesis reaction was monitored by GPC. The two peaks inFIG. 18 indicated that there were two distinct weight fractions ofpolystyrene formed. The M_(n), M_(w), M_(z), M_(Z+1), polydispersity,M_(z)/M_(w), and M_(z+1)/M_(w) of the polystyrene are shown in Table 4.The M_(p) of the first peak in FIG. 18 was found to be about 59,596g/mol. The M_(p) of the second peak in FIG. 18 was found to be about28,619 g/mol.

TABLE 4 Properties Polystyrene M_(n) 28,396 g/mol M_(w) 29,174 g/molM_(z) 29,895 g/mol M_(z+1) 30,598 g/mol Polydispersity 1.027385M_(z)/M_(w) 1.024739 M_(z+1)/M_(w) 1.048810

The polystyrene formed then acted as an initiator to initiate thepolymerization with β-farnesene to form a polystyrene-1,4-polyfarnesenedi-block copolymer. The GPC curve of the di-block copolymer is shown inFIG. 19. The progress of the di-block copolymer synthetic reaction wasmonitored by GPC. The three peaks in FIG. 19 indicated that there werethree distinct weight fractions in the di-block copolymer reactionsolution. The M_(n), M_(w), M_(p), M_(z), M_(z+1), polydispersity,M_(z)/M_(w), and M_(z+1)/M_(w) of the di-block copolymer are shown inTable 5. The M_(p) of the first peak in FIG. 19, corresponding topolystyrene-1,4-polyfarnesene-polystyrene, was found to be about 141,775g/mol. The M_(p) of the second peak in FIG. 19, corresponding to thedi-block copolymer, was found to be about 63,023 g/mol. The molecularweight of 1,4-polyfarnesene in the di-block copolymer was calculated tobe about 35,000 g/mol. The M_(p) of the third peak in FIG. 19,corresponding to polystyrene, was found to be about 29,799 g/mol.

TABLE 5 Polystyrene-1,4-polyfarnesene Properties Di-block CopolymerM_(n) 29,434 g/mol M_(w) 30,345 g/mol M_(D) 29,799 g/mol M_(z) 31,172g/mol M_(z+1) 31,936 g/mol Polydispersity 1.030949 M_(z)/M_(w) 1.027264M_(z+1)/M_(w) 1.052449

The polystyrene-1,4-polyfarnesene di-block copolymer was further coupledto form Example 4. FIG. 20 shows the GPC curve of Example 4. Themolecular weight and polydispersity of Example 4 were determined by GPC.The three peaks in FIG. 20 indicated that there were three distinctweight fractions for the coupling product formed. The M_(n), M_(w),M_(z), M_(z+1), polydispersity, M_(z)/M_(w), and M_(z+1)/M_(w) of thecoupling product are shown in Table 6. The M_(p) of the first peak inFIG. 20, corresponding to Example 4, was found to be about 138,802g/mol. Example 4 was obtained in about 10% of the coupling product. Thenumber of farnesene monomer units in Example 4 was calculated to beabout 300. The M_(p) of the second peak in FIG. 20, which corresponds topolystyrene-1,4-polyfarnesene di-block copolymers, was found to be about63,691 g/mol. The M_(p) of the third peak in FIG. 20, corresponding topolystyrene, was found to be about 29,368 g/mol.

TABLE 6 Properties Example 4 M_(n) 138,240 g/mol M_(w) 142,147 g/molM_(z) 146,636 g/mol M_(z+1) 151,848 g/mol Polydispersity 1.028264M_(z)/M_(w) 1.031576 M_(z+1)/M_(w) 1.068242

FIG. 21 shows the ¹³C NMR spectrum of Example 4. Peaks at 77.68 ppm and76.83 ppm were peaks of associated with the deuterated chloroform usedfor collecting the ¹³C NMR spectrum. Other peaks in FIG. 21 were peaksassociated with 1,4-polyfarnesene and polystyrene. The characteristicpeak identifying 1,4-polyfarnesene at 139.26 ppm was present in FIG. 21,indicating the presence of 1,4-polyfarnesene in Example 4.

FIG. 22 shows the ¹H NMR spectrum of Example 4. Peaks at 4.85 ppm and4.81 ppm were peaks associated with 3,4-microstructure. Peaks at 5.10ppm, 5.12 ppm, and 5.14 ppm were peaks associated with 1,4- and3,4-microstructures. Based on the areas under the peaks of FIG. 22,about 3% of farnesene units in Example 4 was found to have3,4-microstructure.

The DSC curve of Example 4 is shown in FIG. 23. The thermalcharacteristics of Example 4 were measured by DSC. The T_(g) of1,4-polyfarnesene in Example 4 was found to be about −76° C. The T_(g)of polystyrene in Example 4 was found to be about 96° C. No otherthermal event was detected between −175° C. and 75° C.

The TGA curve of Example 4 measured in air is shown in FIG. 24. Thedecomposition temperature of Example 4 in air was determined by TGA. The1% weight loss of Example 4 in air was recorded at 307° C. and the 5%weight loss of Example 4 in air was recorded at 333° C.

The tensile test results of Example 4 are shown in FIG. 25. The tensilestrength of Example 4 was measured by a tensile test. Example 4 wasstiff but yielded. As shown in FIG. 25, the elongation at break ofExample 4 was found to be about 425% with a maximum tensile strength ofabout 152 psi. The modulus of Example 4 was calculated to be about 31.9kpsi. Stress at 330% elongation of Example 4 was about 122 psi.

Example 4 was observed to be tacky. The lap test results of Example 4,due to an adhesive failure, are shown in FIG. 26. The adhesive energy ofExample 4 was found to be about 2,928,000 J/m² with a peak stress ofabout 134,000 N/m².

Example 5 Polystyrene-3,4-polyfarnesene-polystyrene

To a first dried three neck reactor under argon atmosphere, a pre-dried12% solution of β-farnesene in cyclohexane was added. To a second driedthree neck reactor under argon atmosphere, a pre-dried solution of 10%styrene in cyclohexane was added. Afterwards, 141.1 g of the styrenesolution (i.e., 14.82 g of styrene) was transferred to a dried reactorunder argon atmosphere. A mixture of n-butyl lithium (5.84×10⁻⁴ mol) andTMEDA (5.02×10⁻⁴ mol) was added into the reactor as an initiator, andthe reactor was heated at about 50° C. for about 16 hours, until allstyrene was consumed, as monitored by GPC. Then, 143.07 g of β-farnesenesolution (i.e., 15.74 g of β-farnesene) was transferred to the reactorunder argon atmosphere. The reaction was allowed to react untilcompletion for about 16 hours, as monitored by GPC. Dichlorosilanecoupling agent was then added into the reactor in three equal aliquots,such that the mole ratio of Li to Cl was 1:2. The reaction mixture wasallowed react until completion as indicated by a color change fromyellow to clear in the reactor. Example 5 was precipitated from thereaction mixture by a 1% solution of t-butyl catachol in ethanol. Afterdrying in a vacuum oven at about 60° C. for about 2 hours, Example 5 waskept under vacuum for about 16 hours. Afterwards, Example 5, collectedat 28.75 g (yield 96%), was stored in a refrigerator to prevent anycrosslinking before characterization.

The GPC curve of polystyrene is shown in FIG. 27. The progress ofsynthesizing polystyrene was monitored by GPC. The two peaks in FIG. 27indicated that there were two distinct weight fractions of polystyrene.The M_(n), M_(w), M_(z), M_(Z+1), polydispersity, M_(z)/M_(w), andM_(z+1)/M_(w) of polystyrene are shown in Table 7. The M_(p) of thefirst peak in FIG. 27 was found to be about 65,570 g/mol. The M_(p) ofthe second peak in FIG. 27 was found to be about 32,122 g/mol.

TABLE 7 Properties Polystyrene M_(n) 27,915 g/mol M_(w) 30,898 g/molM_(z) 32,608 g/mol M_(z+1) 33,819 g/mol Polydispersity 1.106849M_(z)/M_(w) 1.055361 M_(z+1)/M_(w) 1.094557

The polystyrene formed then acted as an initiator to initiate thepolymerization with β-farnesene to form a polystyrene-3,4-polyfarnesenedi-block copolymer. The GPC curve of the di-block copolymer is shown inFIG. 28. The progress of the di-block copolymer synthesis was monitoredby GPC. The three peaks in FIG. 28 indicated that there were threedistinct weight fractions in the di-block copolymer reaction solution.The M_(n), M_(w), M_(z), M_(z+1), polydispersity, M_(z)/M_(w), andM_(z+1)/M, of the di-block copolymer are shown in Table 8. The M_(p) ofthe first peak in FIG. 28, corresponding topolystyrene-3,4-polyfarnesene-polystyrene, was found to be about 174,052g/mol. The M_(p) of the second peak in FIG. 28, corresponding to thedi-block copolymer, was found to be about 86,636 g/mol. The molecularweight of 3,4-polyfarnesene in the di-block copolymer was calculated tobe about 54,000 g/mol. The M_(p) of the third peak in FIG. 28,corresponding to polystyrene, was found to be about 33,955 g/mol.

TABLE 8 Polystyrene-3,4-polyfarnesene Properties Di-block CopolymerM_(n) 27,801 g/mol M_(w) 31,379 g/mol M_(z) 33,539 g/mol M_(z+1) 35,033g/mol Polydispersity 1.128697 M_(z)/M_(w) 1.068833 M_(z+1)/M_(w)1.116447

The polystyrene-3,4-polyfarnesene di-block copolymer was further coupledto form Example 5. FIG. 29 shows the GPC curve of Example 5. Themolecular weight and polydispersity of Example 5 were determined by GPC.The three peaks in FIG. 29 indicated that there were three distinctweight fractions for the coupling product formed. The M_(n), M_(w),M_(z), M_(z+1), polydispersity, M_(z)/M_(w), and M_(z+1)/M_(w) ofExample 5 are shown in Table 9. The M_(p) of the first peak in FIG. 29,corresponding to Example 5, was found to be about 148,931 g/mol. Example5 was obtained at about 33% of the coupling product. The number offarnesene monomer units in Example 5 was calculated to be about 300. Thepeak molecular weight of the blocks in Example 5 was found to be about32,000-108,000-32,000 g/mol. The M_(p) of the second peak in FIG. 29,corresponding to the polystyrene-3,4-polyfarnesene di-block copolymer,was found to be about 81,424 g/mol. The M_(p) of the third peak in FIG.29, corresponding to polystyrene, was found to be about 32,819 g/mol.

TABLE 9 Properties Example 4 M_(n) 28,179 g/mol M_(w) 30,815 g/mol M_(z)32,590 g/mol M_(z+1) 33,905 g/mol Polydispersity 1.093554 M_(z)/M_(w)1.057606 M_(z+1)/M_(w) 1.100250

FIG. 30 shows the ¹³C NMR spectrum of Example 5. Peaks at 77.72 ppm,77.29 ppm, and 76.87 ppm were peaks of associated with the deuteratedchloroform used for collecting the ¹³C NMR spectrum. Other peaks in FIG.30 were peaks associated with 3,4-polyfarnesene and polystyrene. Thecharacteristic peak identifying 1,4-polyfarnesene at 139.05 ppm wasabsent in FIG. 30, indicating a regular microstructure of Example 5.

FIG. 31 shows the ¹H NMR spectrum of Example 5. Peaks at 4.85 ppm and4.81 ppm were peaks associated with 3,4-microstructure. Peaks at 5.15ppm and 5.13 ppm were peaks associated with 1,4- and3,4-microstructures. Based on the areas under the peaks of FIG. 31,about 5% of farnesene units in Example 5 was found to have1,4-microstructure.

The DSC curve of Example 5 is shown in FIG. 32. The thermalcharacteristics of Example 5 were measured by DSC. The T_(g) of3,4-polyfarnesene in Example 5 was found to be about −72° C. The T_(g)of polystyrene in Example 5 was found to be about 94° C. No otherthermal event was detected between −175° C. and 75° C.

The TGA curve of Example 5 measured in air is shown in FIG. 33. Thedecomposition temperature of Example 5 in air was determined by TGA. The1% weight loss of Example 5 in air was recorded at 240° C. and the 5%weight loss of Example 5 in air was recorded at 327° C.

The tensile test results of Example 5 are shown in FIG. 34. The tensilestrength of Example 5 was measured by a tensile test. Example 5 wasstiff but yielded. As shown in FIG. 34, the elongation at break ofExample 5 was found to be about 175% with a maximum tensile strength ofabout 768 psi. The modulus of Example 5 was calculated to be about 39.5kpsi.

Example 5 was further purified by repeated extraction with solventhexane 4 times. The GPC curve of the purified Example 5 is shown in FIG.35. The extraction of Example 5 from the coupling product was evaluatedby GPC. After the extraction, Example 5, shown as the first peak in FIG.35, was increased to about 60% of the extracted product. Thepolystyrene-3,4-polyfarnesene di-block copolymer, shown as the secondpeak in FIG. 35, was reduced to about 30% of the extracted product.Polystyrene, shown as the third peak in FIG. 35, was reduced to about10% of the extracted product.

The GPC curve of the extraction solvent hexane is shown in FIG. 36.After the extraction, Example 5 existed in very low amount in theextraction solvent, shown as the first peak in FIG. 36. A significantamount of the polystyrene-3,4-polyfarnesene di-block copolymer wasextracted to the extraction solvent, shown as the second peak in FIG.36. A majority of polystyrene was extracted to the extraction solvent,shown as the third peak in FIG. 36.

The tensile test results of the purified Example 5 are shown in FIG. 37.The tensile strength of the purified Example 5 was measured by a tensiletest. Example 5 was soft and readily yielded. As shown in FIG. 37, theelongation at break of the purified Example 5 was found to be about 550%with a maximum tensile strength of about 340 psi. The modulus of thepurified Example 5 was calculated to be about 65.9 kpsi. Stress at 300%elongation of the purified Example 5 was found to be about 133 psi.

The purified Example 5 was observed to be highly tacky. The lap testresults of the purified Example 5, due to an adhesive failure, are shownin FIG. 38. The adhesive capability of the purified Example 5 wasmeasured by a lap test. The adhesive energy of the purified Example 5was found to be about 1,787,000 J/m² with a peak stress of about 120,000N/m².

Example 6

Example 6 was formed by the vulcanization of Example 1. To formulate thereaction mixture, 62.7 g of Example 1 was mixed with 3.20 g zinc oxide,1.25 g stearic acid, 0.94 g Rubbermakers Sulfur MC-98, 0.13 gAccelerator TMTD (tetramethylthiuram disulfide), and 0.63 g AcceleratorOBTS (N-oxydiethylene-2-benzothiazole sulfenamide). Zinc oxide, stearicacid, Rubbermakers Sulfur MC-98, Accelerator TMTD, and Accelerator OBTSwere obtained from Akrochem Corporation, Akron, Ohio. The mixture wasthen placed in a vulcanization mold and degassed at about 140° C. forabout 30 minutes. After degassing, the mixture was cured at about 170°C. for about 15 minutes. After de-molding, Example 6, an elastic solid,was collected at 70.4 g (yield 81%).

The tensile test results of Example 6 are shown in FIG. 39. The tensilestrength of Example 6 was measured by a tensile test. As shown in FIG.39, the elongation at break of Example 6 was about 38% with a maximumtensile strength of about 16 psi. The modulus of Example 6 wascalculated to be about 58 psi.

Example 7

Example 7 was formed by the vulcanization of Example 2. Example 7 wassynthesized similarly according to the procedure for Example 6 exceptthat Example 1 was replaced by 60.3 g Example 2. The net weight ofExample 7 was found to be 68.1 g (yield 78%).

The tensile test results of Example 7 are shown in FIG. 40. The tensilestrength of Example 7 was measured by a tensile test. As shown in FIG.40, the elongation at break of Example 7 was found to be about 25% witha maximum tensile strength of about 10 psi. The modulus of Example 7 wascalculated to be about 66 psi.

While the invention has been described with respect to a limited numberof embodiments, the specific features of one embodiment should not beattributed to other embodiments of the invention. No single embodimentis representative of all aspects of the invention. In some embodiments,the compositions or methods may include numerous compounds or steps notmentioned herein. In other embodiments, the compositions or methods donot include, or are substantially free of, any compounds or steps notenumerated herein. Variations and modifications from the describedembodiments exist. Finally, any number disclosed herein should beconstrued to mean approximate, regardless of whether the word “about” or“approximately” is used in describing the number. The appended claimsintend to cover all those modifications and variations as falling withinthe scope of the invention.

1. A hydrogenated polyfarnesene prepared by: (a) polymerizing afarnesene in the presence of a catalyst to form a polyfarnesene; and (b)hydrogenating at least a portion of double bonds in the polyfarnesene inthe presence of a hydrogenation reagent to form the hydrogenatedpolyfarnesene, wherein the polyfarnesene prepared by step (a) hasformula (X′):

wherein n is from 1 to about 100,000; m is from 0 to about 100,000; Xhas one or more of formulae (I′)-(VIII′):

Y has formula (IX′):

wherein R′ has formula (XI):

R² has formula (XII):

R³ has formula (XIII):

R⁴ has formula (XIV):

wherein each of R⁵, R⁶, R⁷ and R⁸ is independently H, alkyl, cycloalkyl,aryl, cycloalkenyl, alkynyl, heterocyclyl, alkoxy, aryloxy, carboxy,alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl,acyloxy, nitrile or halo, and wherein formula (I′) is in an amount of atmost about 80 wt. % and formula (II′) is in an amount from about 5 wt. %to about 99 wt. %, based on a total weight of the polyfarnesene.
 2. Thehydrogenated polyfarnesene of claim 1, wherein a portion of the doublebonds in the polyfarnesene is hydrogenated.
 3. The hydrogenatedpolyfarnesene of claim 1, wherein the polyfarnesene is completelyhydrogenated.
 4. The hydrogenated polyfarnesene of claim 1, wherein thefarnesene is copolymerized with a vinyl monomer to form a farnesenecopolymer.
 5. The hydrogenated polyfarnesene of claim 4, wherein thevinyl monomer is styrene.
 6. The hydrogenated polyfarnesene of claim 5,wherein the polyfarnesene is a block copolymer.
 7. The hydrogenatedpolyfarnesene of claim 1, wherein the farnesene is α-farnesene orβ-farnesene or a combination thereof.
 8. The hydrogenated polyfarneseneof claim 1, wherein the farnesene is prepared by a microorganism.
 9. Thehydrogenated polyfarnesene of claim 1, wherein the farnesene is derivedfrom a monosaccharide, disaccharide, polysaccharide or a combinationthereof.
 10. The hydrogenated polyfarnesene of claim 1, wherein thefarnesene is derived from glucose, galactose, mannose, fructose, ribose,sucrose, lactose, maltose, trehalose, cellobiose, starch, glycogen,cellulose, chitin or a combination thereof.
 11. The hydrogenatedpolyfarnesene of claim 1, wherein the catalyst comprises anorganolithium reagent, a Ziegler-Natta catalyst, a Kaminsky catalyst, ora metallocene catalyst.
 12. The hydrogenated polyfarnesene of claim 11,wherein the catalyst comprises an organolithium reagent and1,2-bis(dimethylamino)ethane.
 13. The hydrogenated polyfarnesene ofclaim 12, wherein the organolithium reagent is n-butyl lithium orsec-butyl lithium.
 14. The hydrogenated polyfarnesene of claim 1,wherein the hydrogenation reagent is hydrogen in the presence of ahydrogenation catalyst.
 15. The hydrogenated polyfarnesene of claim 14,wherein the hydrogenation catalyst is 10% Pd/C.
 16. The hydrogenatedpolyfarnesene of claim 1, wherein m is from 1 to about 100,000; and amole percent ratio of X to Y is from about 1:4 to about 100:1.
 17. Thehydrogenated polyfarnesene of claim 1, wherein m is 0 and thepolyfarnesene is a farnesene homopolymer.
 18. The hydrogenatedpolyfarnesene of claim 1, wherein m is from 1 to about 100,000 and thepolyfarnesene is a random farnesene interpolymer.
 19. The hydrogenatedpolyfarnesene of claim 1, wherein m is from 1 to about 100,000 and thepolyfarnesene is a block farnesene interpolymer.
 20. The hydrogenatedpolyfarnesene of claim 19, wherein the block farnesene interpolymeraccording to formula X′ comprises one block of one or more X and twoblocks each of one or more Y and wherein the one block of one or more Xis between the two blocks each of one or more Y.